Pultrusion process for long fiber-reinforced nylon composites
BACKGROUND OF THE INVENTION 
     The invention relates to a pultrusion processing method of nylon composites which uses the technology of long fiber-reinforced nylon anionic polymerization to produce nylon composite materials. The conventional pultrusion processing method basically employs thermosetting resins with low viscosity, such as unsaturated polyester, phenolic resins, epoxy resins and the like. For these thermosetting resin systems, many commercialized pultrusion machines and processes were developed to carry out commercialized production and to manufacture various finished products of thermoset plastic composites having structural strength. 
     Compared to short fiber-reinforced composites, thermoplastic composites are easy to store, with a long shelf life, the ability to be second molded and possessing mechanical strength. Therefore nations with advanced industrial technology are eager to research and develop the market for long fiber-reinforced thermoplastic composites. Traditionally, due to its excellent performance, short fiber-reinforced nylon composites have been broadly used. Similarly in various types of long fiber-reinforced thermoplastic composites, nylon composites whose development and product application research are also considered important are substantially potential generation of fiber-reinforced thermoplastic composites. In the preparation method for long fiber-reinforced thermoplastic composites, commercialized preparation methods are multi-step indirect methods. Wherein after polymerized thermo plastics are melted or dissolved, the final semi-finished products of thermoplastic composite materials are molded by means of autoclaving or impregnating reinforced fiber in second molding. For the autoclaved thermoplastic composites, because of the high viscosity of melt polymers, reinforced fiber cannot be wetted well enough. This lowers the bonding strength of interfaces between resin matrix and reinforced fiber which therefore dramatically reduces the composites mechanical strength and performance. The impregnation method of dissolved polymer solution which is necessary to dry away the solvent in impregnated composites is complex, wastes power and easily results in environment pollution. Therefore the preparation method for fiber-reinforced thermoplastic composites by impregnation in a polymer solution is not ideal. 
     See &#34;RIM-Pultrusion of Thermoplastic Matrix Composites&#34; by H. Ishida and G. Rotter in 43rd Annual Conference, Composite Institute, The Society of the Plastic Industry, 1988. Ishida et al. used caprolactam as reactant monomer, sodium hydride as a catalyst for anionic polymerization and phenyl isocyanate as initiator. After sodium hydride and phenyl isocyanate were reacted with a caprolactam catalyst composition and an initiator composition they were formed respectively and then individually added into the resin tanks of the high temperature reaction injection molding machine. After the catalyst composition was mixed with the initiator composition at high pressure, the mixture was injected into a resin impregnating tank to impregnate the glass fiber roving. Thereafter the fiber impregnated with nylon 6 reactant was drawn into a hot mold to polymerize nylon matrix and glass fiber-reinforced nylon 6 composites were obtained. However, the data of any mechanical strength of nylon 6 composites are not disclosed in this literature, therefore it is not understood whether the processing method described by Ishida et al. is possible in practice. 
     A method using in-situ pultrusion processing to produce fiber-reinforced thermoplastic composites is disclosed by J. S. HWANG and S. N. TONG et al. in 44th Annu. Conf. RP/C, SPI, 8-C(1988), wherein the main objective is to develop a new thermoplastic system and novel in-situ pultrusion processing equipment. In this paper, ABS resin is obtained by reacting liquid acrylonitrile-butadiene copolymer with styrene monomer, then this resin is injected into a heating mold to prepreg the reinforced fiber and cure it. During researching, it is found that the low viscosity of resins can make the fiber well prepreged, and it is important that the final product be remolded by heating. This method provides the resins which are both safe and convenient for treatment. 
     A pultrusion method to produce heat resistant carbon fiber-reinforced polyether imide composites having high performance is disclosed by Maywood L. Wilson and John D. Buckley et al. in 44th Annu. Conf. RP/C, SPI, 8-C(1988). The difference between this pultrusion processing and conventional pultrusion processing of thermoset resins is that monomer reactant and solvent are not produced during the polymerization in the pultrusion mold. Besides, in order to wet and cure reinforced fiber, the viscosity of conventional thermoset resins is in the range of about 500-1,000 cps and the temperature of the pultrusion mold is about in 300°-400° F. However, in the thermoplastic pultrusion processing method, the viscosity may be up to 1,000,000 cps or more and the temperature may be 800° F. 
     The same RIM-Pultrusion molding method described above is continuously used to produce nylon composites by Xin Xing and Hatsuo Ishida in 1990 Annu. Conf., Composite Institute, The Society of the Plastic Industry, wherein nylon initiator in reactants of polymerization is changed with the pre-polymer obtainable by reacting polypropylene-oxide having the molecular weight of 4000 with hexamethylene diisocyanate. However, it doesn&#39;t show any data about common mechanical properties of finished products made of nylon composites. So the processing workability and the practical possibility of nylon composites can&#39;t be confirmed. 
     &#34;A Study on the Properties of Continuous Fiber-Reinforced Nylon 6 Resin Composite Materials&#34; is published by Chen-chi Ma and Meng-sung Yin in ROC Polymer Seminar Meeting 1988, wherein the polymerization of nylon 6 is conducted by the method of hydrolytic polymerization. 
     SUMMARY OF THE INVENTION 
     The invention relates to a novel method for manufacturing long fiber-reinforced thermoplastic nylon composites. The method is best characterized by saying that after being melted, dehydrated and purified, caprolactam (i.e. the raw material of nylon monomer) is reacted with strong alkali sodium hydride catalyst to form an active catalyst composition, And a co-catalyst composition is formed by melting caprolactum and a pre-polymer co-catalyst with NCO end group. Then the active catalyst composition is mixed with a prepolymer co-catalyst in a continuous mixing device with dry nitrogen gas blanketed at a temperature of 80°-110° C. The reaction mixture with low viscosity between 10 and 1500 cps is injected to a closed reinforced fiber impregnating tank, and after impregnating preheated and dried reinforced fiber, impregnated nylon reaction mixture is drawn into a hot mold by using the pultrusion machine. At the same time, nylon anionic ring-opened polymerization and molding processing are carried out simultaneously and the long fiber-reinforced thermoplastic nylon composites are obtained. The resulting long fiber-reinforced nylon composites, obtained through the monomer with low viscosity as resin matrix, may achieve a thorough wetting effect of fibers so as to reduce the void defects at the interfaces between nylon matrix and reinforced fiber in composites. Therefore the nylon composites produced by this pultrusion processing method of long fiber-reinforced anionic polymeric nylon composites of the invention exhibit the most excellent mechanical strength and performance. 
     In the pultrusion process of the long fiber-reinforced anionic polymerization nylon composites of the invention, the polymerization of nylon matrix uses the anionic ring-opening fast polymerization technique. Therefore the moisture content of the nylon monomer shall be controlled in a state approximately free of water. Before being impregnated with the caprolactam monomer, the reinforced long fiber must be preheated thoroughly to remove moisture, so that nylon anionic polymerization is conducted without problems to obtain well polymerized products of nylon composite materials. 
     In this invention, the moisture content of caprolactam monomer raw materials, according to what the inventors understand, is required to be controlled to less than 500 ppm so as to conduct nylon anionic polymerization without problems. Because the moisture content of caprolactam monomer raw material used in industry is usually above 900-1,000 ppm, it isn&#39;t suitable for a nylon anionic ring-opening polymerization system. In the nylon pultrusion processing procedure of the invention, the moisture content of caprolactam monomer is reduced to be less than 500 ppm, by the technology of reduced pressure distillation, to correspond with the especial requirement of nylon anionic polymerization. 
     Basically, alkali catalysts suitable for nylon anionic ring-opening polymerization system are categorized into three types; the first one is alkali metal elements such as lithium, potassium and sodium etc. or related hydride compounds thereof, the second one is organic metallic derivatives of the first type of catalyst such as butyl lithium, ethyl potassium and propyl sodium, and the third one is a salt formed with Grignard reagent and caprolactam monomer such as bromomagnesium caprolactam salt. The catalysts described above may be used either alone or in a mixture thereof in order to adjust the rate of polymerization. 
     The co-catalysts suitable for the nylon anionic polymerization in this invention are polymeric co-catalysts having an NCO functional group at the end of molecular chain which is obtained by reacting polyglycol compound with diisocyanate compound. During the preparation of polymeric co-catalyst, the ratio of NCO group equivalent number and OH group equivalent number (NCO/OH Index) can be controlled in the range of 1.2-3.0, preferably in the range of 1.5-2.2. Polyglycol can be any polyglycol selected from the group consisting of long chain polyether, polysilicone, polyester, polycaprolactam and hydroxyl terminated polybutadiene having OH end groups or a mixture thereof. Diisocyanate used for the preparation of polymeric cocatalyst can be aliphatic or aromatic diisocyanates, wherein aliphatic diisocyanates are preferable. Aliphatic diisocyanates suitable for the invention are: 
     1. isophrone diisocyanate (IPDI); 
     2. hexamethylene diisocyanate (HDI); 
     3. dicyclohexylmethane diisocyanate; and, 
     4. cyclohexyl diisocyanate. 
     There are many types of fiber-reinforced materials used in commercialized products, for example inorganic glass fiber, carbon fiber and organic polyamide fiber or mixing fiber combining organic and inorganic fiber. But, according to the researching results of the inventors, it is found that inorganic glass fiber and carbon fiber are the most preferable to be used as long fiber reinforcement in the pultrusion processing method of long fiber-reinforced anionic polymerization nylon composites of the invention. The testing standards of mechanical properties of fiber-reinforced nylon composites in the invention are shown as the following: 
     
         ______________________________________                                    
tensile strength       ISO 3268                                           
flexural strength      ASTM D790                                          
Heat distortion temperature                                               
                       ASTM D648                                          
Izod impact strength   ASTM D256                                          
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     BRIEF DESCRIPTION OF THE DRAWINGS 
     FIG. 2.1 is a schematic drawing of a pultrusion processing method of long fiber-reinforced anionic polymerization nylon composites of the invention. 
     FIG. 2.2 is a detailed schematic drawing of a pultrusion processing device design of anionic polymerization nylon of the invention. 
     FIG. 2.3 is a design drawing of the combination of a reinforced fiber impregnation tank and a hot mold in nylon pultrusion processing device of the invention. 
     FIGS. 2.4A-2.4C are scanning electroic microscopic pictures of finished products from the process of the present invention. 
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 
     The following examples will provide detailed illustrations of the technology and objectives of the present invention, but are not intended to limit the claims of the invention. 
     EXAMPLE 1 
     Preparation of Caprolactam Monomer with Low Moisture Content 
     The method of purifying and dehydrating caprolactam in the invention utilizes the technology of reduced pressure and vacuum distillation. The objective of purification and dehydration is to reduce moisture content of caprolactam to below 500 ppm, so that caprolactam monomer can be suitable for use in nylon anionic polymerization. In this example, the treatment amount of purifying and dehydrating caprolactam is 30 Kg/batch. The results are shown in Table 1: 
     
                       TABLE 1                                                     
______________________________________                                    
Resource of caprolactam raw material: industrial solid flake              
caprolactam monomer available from ROC Chemistry Co.                      
Treatment amount of caprolactam: 30 Kg/batch                              
Treatment conditions of purifying and dehydrating caprolactam:            
1. Temperature of caprolactam monomer in distillation tank:               
   145° C.                                                         
2. Reflux time of distillation: reflux 2 hours                            
3. Degree of vacuum in distillation tank: 750 mmHg                        
Moisture content of caprolactam before treatment: 1,000 ppm               
Moisture content of caprolactam after treatment: 280 ppm                  
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     In this example, moisture content of caprolactam may be reduced from 1,000 ppm to 280 ppm in 2 hours by purification under the conditions of reduced pressure and vacuum distillation above, which is suitable to be used in the pultrusion processing of long fiber-reinforced anionic polymerization nylon composites of the invention to satisfy the demand for caprolactam with low moisture content, less than 500 ppm. 
     EXAMPLE 2 
     The pultrusion processing of Long Fiber-Reinforced Anionic Polymerization Nylon Composites 
     After 1000 g (1 mole) of poly-propylene oxide long chain polyether polyglycol having two OH end groups and the molecular weight of 1000 g/mole and 444 g (2 mole) of isophorone diisocyanate (IPDI) are added into reaction tank, mixed well and then is added with 0.06 g of dibutyltin dilaurate to be mixed uniformly, the mixture is heated to 50° C., reacted with stirring for 4 hours at 50° C., and transparent polymeric co-catalyst No. IPPG1000-2 having NCO end groups is obtained. 
     Preparation of Active Caprolactam Sodium Salt Catalyst Composition 
     After caprolactam monomer with low moisture content purified in the same manner as example 1 is heated to 90° C., proper amount (as shown in Table 2.1) of sodium hydride is added and stirred for 20 minutes to form active caprolactam sodium salt catalyst side. Thereafter, the catalyst composition is placed in an active caprolactam sodium salt catalyst composition tank with nitrogen gas blanketing and held at a temperature of 90°-110° C. 
     Preparation of Polymeric Co-Catalyst 
     Caprolactam monomer with low moisture content purified in the same manner as example 1 together with No. IPPG 1000-2 polymeric co-catalyst (the respective amounts as shown in Table 2.1) are added in the polymeric co-catalyst composition tank and heated to a temperature of 90°-110° C. 
     The Pultrusion Processing of Long Fiber-Reinforced Anionic Polymerization Nylon Composites 
     FIG. 2.1 is a schematic drawing of a pultrusion processing method of long fiber-reinforced anionic polymerization nylon composites of the invention. FIG. 2.2 is a detailed schematic drawing of a pultrusion processing device design of anionic polymerization nylon of the invention. FIG. 2.3 is a design drawing of the combination of a reinforced fiber impregnation tank and a hot mold in a nylon pultrusion processing device of the invention. In the pultrusion processing method of long fiber-reinforced anionic polymerization nylon composites of this invention, because the polymerization method of nylon matrix employs anionic fast polymerization method, the polymerization rate of nylon matrix depends on the temperature, concentrations of the catalyst and polymeric co-catalyst in the resin formulation. Besides, the presence of inner and outer moisture of the anionic polymerization system also affects nylon matrix reactivity. Therefore, in the pultrusion method of long fiber-reinforced anionic polymeric nylon composites, reinforced long fiber must be thoroughly preheated and dehydrated to prevent minor moisture adsorbed on the fiber surfaces from being brought into the reaction system. Additionally, during processing, since at high temperatures the mold easily transfers heat energy into the impregnating tank, the resin reactivity may be increased to result in an increase in the viscosity of resin. The gel will be formed at the end of the impregnating tank so as to reduce the impregnating effect into fiber and even clog the mold to break the process. In this invention, one heat-insulating apparatus is inserted between the impregnating tank and the mold, so the junction of the end of the impregnating tank and the mold is held at a temperature below 115° C. and the processing is continuously operated for over 8 hours without problems. In FIG. 2.1, reinforced fibers are preheated in 3 m-long fiber preheating device, preferably at a temperature between 150° C. to 250° C. Active caprolactam sodium salt catalyst composition and co-catalyst composition are mixed in a continuous tubular mixing device with nitrogen gas blanketing at a temperature of 90°-110° C., and the mixing ratio of active caprolactam sodium salt catalyst composition and co-catalyst composition is controlled in 1:0.9-1.1. Thereafter, the reaction mixture with low viscosity is fed into a closed stainless steel reinforced fiber impregnating tank with nitrogen gas blanketing at a temperature of 90°-110±5° C. After reinforced glass long fiber (glass roving available from PPG Co. #247) is impregnated with reaction monomer mixture having low viscosity in impregnating tank and then sent into a hot mold at a temperature of 210±5° C. to conduct nylon anionic polymerization, the polymerized molding material is drawn to become glass long fiber-reinforced nylon composites. The process can be continuously operated for 8 hours under the process conditions as shown in this example, and the pulling rate is about 35 to 40 cm/min (mold length: 1 m). 
     The mechanical properties of the products of glass long fiber-reinforced nylon composites are tested and listed as shown in Table 2.1. In FIG. 2.4, the impregnation and combination of nylon matrix and glass long fiber-reinforced materials in finished products are observed by scanning with an electron microscope which uses No. IPPG 1000-2-10-G75 in Table 2.1 as a sample of glass long fiber-reinforced nylon composite finished product. From FIG. 2.4, the resulting nylon composites manufactured by the pultrusion process of long fiber-reinforced nylon designed by this invention are sure to have the thorough wetting effect of nylon matrix to reinforced glass long fiber. At the same time there is an excellent combined effect at the interfaces between nylon matrix and reinforced glass long fiber. 
     
                                           TABLE 2.1                               
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Print product IPPG1000                                                    
                     1PPG1000                                             
                            1PPG1000                                      
                                   1PPG1000                               
                                          1PPG1000                        
                                                 1PPG1000                 
                                                        1PPG1000          
number                                                                    
2-10-G79                                                                  
2-10-G75                                                                  
2-10-G77                                                                  
2-10-G75                                                                  
2-6-G73                                                                   
2-6-G64                                                                   
2-3-G74                                                                   
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Polymeric co-catalyst                                                     
              IPPG1000-2                                                  
                     IPPG1000-2                                           
                            IPPG1000-2                                    
                                   IPPG1000-2                             
                                          IPPG1000-2                      
                                                 IPPG1000-2               
                                                        IPPG1000-2        
number                                                                    
NaH amount (g/1 Kg                                                        
              0.13   0.13   0.15   0.15   0.2    0.2    0.3               
reaction mixture)                                                         
Temperature of reaction                                                   
              110    110    105    105    100    100    90                
mixture (°C.)                                                      
Viscosity of reaction                                                     
              150    100     40     40     30     15     14               
mixture (cps)                                                             
Weight fraction of                                                        
               30     20     10     10     6      6      3                
polymeric co-catalyst                                                     
in the nylon matrix (%)                                                   
Mechanical Properties:                                                    
Type of reinforced long fiber                                             
              Glass fiber                                                 
                     Glass fiber                                          
                            Glass fiber                                   
                                   Glass fiber                            
                                          Glass fiber                     
                                                 Glass fiber              
                                                        Glass fiber       
Content of fiber (weight %)                                               
              79.2   77.1   75.5   73.5   72.9   69.1   74.5              
Tensile modulus (MPa)                                                     
              47880  46000  44198  42322  43214  41050  44310             
Tensile strength (MPa)                                                    
              1305   1185   1053   950    1001   805    1115              
Flexural modulus (MPa)                                                    
              42150  41700  40041  37800  37618  32908  40800             
Flexural strength (MPa)                                                   
              518    504    495    457    490    445    501               
Notch Izod impact strength                                                
              57.1   55.0   53.3   50.0   52.1    48    52.8              
(Ft. lb/inch)                                                             
Heat distortion temperature                                               
              197    199    200    200    202    201    202               
(°C., 264 psi)                                                     
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     FIG. 2.1 The schematic drawing of a pultrusion processing method of long fiber-reinforced anionic polymerization nylon composites. 
     The description of each designated mark is: 
     1. Fiber roving 
     2. Fiber guide 
     3. Fiber preheating and drying device (3 m in length, inner temperature: 150°-250° C.) 
     4. Dry hot air inlet (temperature of hot air: 150°-250° C.) 
     5. Dry hot air outlet 
     6. Closed stainless steel fiber impregnating tank (with dry nitrogen gas blanketing the temperature of the tank body: controlled in 90°-110° C.) 
     7. Dry nitrogen gas inlet 
     8. Heat-insulating liner (3 mm-10 mm in thickness) 
     9. Active caprolactam sodium salt catalyst composition tank 
     10. Polymeric co-catalyst composition tank 
     11. Continuous mixing device with dry nitrogen gas blanketing 
     12. Stoichiometric controlling valve 
     13. Feed controlling valve 
     14. Holding feed tube (temperature: controlled in 
     15. Heating mold (mold temperature: 170°-210±5° C.) 
     16. Tractor 
     17. Cutter 
     18. Finished product 
     FIG. 2.2 The detailed schematic drawing of a pultrusion device design of long fiber-reinforced anionic polymeric nylon. 
     The description of each designated mark is: 
     1. Fiber preheating and drying apparatus (3 m in length, temperature: held in 150°-250° C. by an electric heater) 
     2. Reinforced fiber 
     3. Dry hot air inlet (temperature of hot air: 150°-250° C.) 
     4. Dry hot air outlet 
     5. Closed stainless steel fiber impregnating tank (with dry nitrogen gas blanketing, the temperature of tank body: controlled in 90°-110° C. by an electric heater) 
     6. Dry nitrogen gas inlet 
     7. Overflow hole 
     8. Heat-insulating liner (3 mm-10 mm in thickness) 
     9. Active caprolactam sodium salt catalyst side tank (with dry nitrogen gas blanketing, the temperature of tank body: controlled in 90°-110° C. by silicone oil heating system) 
     10. Polymeric co-catalyst side tank (with dry nitrogen gas, the temperature of the tank body: controlled in 90°-110° C. by silicone oil heating system) 
     11. Continuous mixing device with dry nitrogen gas blanketing 
     12. Stoichiometric controlling valve 
     13. Reaction mixture feed controlling valve 
     14. Holding feed tube 
     15. Hot mold 
     16. Finished product of nylon composite 
     FIG. 2.3 The design drawing of the combination of a reinforced fiber impregnating tank and a hot mold. 
     The description of each designated mark is: 
     1. Reaction mixture inlet 
     2. Heat-insulating liner (3 mm-10 mm in thickness, the temperature of the end of fiber impregnating tank in position 5 of FIG. 2.3: held below 115° C.) 
     3. Closed stainless steel fiber impregnating tank (the temperature of tank body: controlled in 90°-110° C.) 
     4. Upper and lower hot molds by an electric heater 
     5. Orifice gates at the end of fiber impregnating tank 
     6. Reinforced long fiber 
     7. 5°&lt;H&lt;25° 
     8. 8 cm&lt;L&lt;20 cm 
     EXAMPLE 3 
     The Preparation of Polymeric Co-Catalyst 
     After 1 mole of poly-propylene oxide long chain polyether polyglycol having two OH end groups and the molecular weight of 400, 2,000 and 4,000 (g/mole) together with 2 mole of isophorone diisocyanate are added into the reaction tank to be thoroughly mixed with stirring, then 0.06 g of dibutyltin dilaurate is added and mixed uniformly, the mixture is heated to 50° C., stirred at 50° C. for 4 hours and polymeric co-catalysts Nos. IPPG400-2, IPPG2000-2 and IPPG4000-2 are obtained respectively. 
     The Preparation of Active Caprolactam Sodium Salt Catalyst Composition 
     After dehydrated and purified caprolactam monomer with low moisture content, less than 500 ppm, is heated to 90° C., proper amount (as shown in Table 3.1) of sodium hydride is added and stirred to form an active caprolactam sodium salt catalyst composition. Thereafter, the catalyst composition is placed in active caprolactam sodium salt catalyst composition tank with nitrogen gas and held at a temperature of 90°-110° C. 
     The Preparation of Polymer Co-Catalyst Composition 
     Dehydrated and purified caprolactam monomer with low moisture content, less than 500 ppm, together with polymeric co-catalyst (the types and amounts as shown in Table 3.1) are added, placed into polymeric co-catalyst composition tank with nitrogen gas and heated to a temperature of 90°-110° C. 
     The Pultrusion Processing of Long Fiber-Reinforced Anionic Polymerization Nylon Composites 
     The glass long fiber-reinforced nylon composites with the pulling rate of 34 to 38 cm/min (mold length: 1 m, mold temperature: 200°±5° C.) are obtained by means of the same pultrusion processing method of nylon composites as shown in FIG. 2.1 using reinforced glass long fiber of glass roving available from PPG Co. #247 and the formulation of nylon matrix as shown in Table 3.1 under the reaction conditions in Table 3.1. In this example, the mechanical properties of the products of glass long fiber-reinforced nylon composites manufactured by pultrusion processing are tested and listed as shown in Table 3.1. 
     
                                           TABLE 3.1                               
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Finished product    IPPG400-2                                             
                           TPPG400-2                                      
                                  IPPG2000-2                              
                                         IPPG4000-2                       
number                                                                    
30-G74                                                                    
10-G75                                                                    
10-G76                                                                    
10-G77                                                                    
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Polymeric co-catalyst number                                              
                    IPPG400-2                                             
                           IPPG400-2                                      
                                  IPPG2000-2                              
                                         IPPG4000-2                       
NaH amount (G/1 Kg reaction mixture)                                      
                    0.15   0.13   0.2    0.3                              
Temperature of reaction mixture (°C.)                              
                     90    105    100    100                              
Temperature of reaction mixture (cps)                                     
                    1100   250    100    220                              
Weight fraction of polymeric co-catalyst                                  
                     30     10     10     10                              
in the nylon matrix (%)                                                   
Mechanical properties                                                     
Type of reinforced long fiber                                             
                    Glass fiber                                           
                           Glass fiber                                    
                                  Glass fiber                             
                                         Glass fiber                      
Content of fiber (weight %)                                               
                    73.5   74.6   76.1   76.8                             
Tensile modulus (MPa)                                                     
                    --     44500  44850  --                               
Tensile strength (MPa)                                                    
                    --     1069   1180   --                               
Flexural modulus (MPa)                                                    
                    --     39800  --     --                               
Flexural strength (MPa)                                                   
                    --     488    --     --                               
Notch izod impact strength                                                
                    54.2   51.0   56.1   55.8                             
(Ft. lb/inch)                                                             
Heat distortion temperature                                               
                    194    197    202    204                              
(°C., 264 psi)                                                     
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     EXAMPLE 4 
     The Preparation of Polymeric Co-Catalyst 
     After 1 mole of polytetramethylene glycol (PTNG) long chain polyether polyglycol having two OH end groups and the molecular weight of 1,000 and 2,000 (g/mole) together with 2 moles of isophorone diisocyanate are added into the reaction tank to be thoroughly stirred, then supplemented with 0.03 g of dibutyltin dilaurate and mixed uniformly. The mixture is heated to 50° C., reacted with stirring at 50° C. for 4 hours and polymeric co-catalyst Nos. IPTG1000-2 and IPTG2000-2 are obtained respectively. 
     The Preparation of Active Caprolactam Sodium Salt Catalyst Composition 
     After dehydrated and purified caprolactam monomer with low moisture content, less than 500 ppm, is heated to 90° C., proper amount (as shown in Table 4.1) of sodium hydride is added and stirred to form active caprolactam sodium salt catalyst composition. Thereafter, the catalyst composition is placed in active caprolactam sodium salt catalyst composition tank with nitrogen gas and held at a temperature of 90°-110° C. 
     The Preparation of Polymeric Co-Catalyst Composition 
     Dehydrated and purified caprolactam monomer with low moisture content, less than 500 ppm, of purified and dehydrated caprolactam monomer together with polymeric co-catalyst (the types and amounts as shown in Table 4.1) are added, placed into polymeric co-catalyst side tank with nitrogen gas and heated to a temperature of 90°-110° C. 
     The Pultrusion Processing of Long Fiber-Reinforced Anionic Polymerization Composites 
     The carbon fiber-reinforced nylon composites with the pulling rate of 35 to 40 cm/min (mold length: 1 m, mold temperature: 210±5° C.) are obtained by means of the same pultrusion processing method of nylon composites as shown in FIG. 2.1 using Besfight HTA reinforced carbon fiber available from Toho Rayon Co. (Filament count=12,000, Yield=800 Tex) and the formulation of nylon matrix as shown in Table 4.1 under the reaction conditions in Table 4.1. In this example, the mechanical properties of the products of carbon long fiber-reinforced nylon composites manufactured by pultrusion processing are tested and listed as shown in Table 4.1. 
     
                       TABLE 4.1                                                   
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Finished product  IPTG1000-2 IPTG2000-2                                   
number                                                                    
10-C75                                                                    
10-C76                                                                    
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Polymeric co-catalyst number                                              
                  IPTG1000-2 IPTG2000-2                                   
NaH amount (g/1 Kg reaction                                               
                  0.2        0.2                                          
mixture)                                                                  
Temperature of reaction mixture                                           
                  110        110                                          
(°C.)                                                              
Viscosity of reaction mixture                                             
                   55         65                                          
(cps)                                                                     
Weight fraction of polymeric                                              
                   15         10                                          
co-catalyst                                                               
in the nylon matrix (%)                                                   
Mechanical properties:                                                    
Type of reinforced long fiber                                             
                  Carbon     Carbon                                       
                  fiber      fiber                                        
Content of fiber (weight %)                                               
                  75.1       76.2                                         
Tensile strength (MPa)                                                    
                  1630       1785                                         
Heat distortion temperature                                               
                  204        206                                          
(°C., 264 psi)                                                     
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     EXAMPLE 5 
     The Preparation of a Polymeric Co-Catalyst 
     Polysilicone long chain polyglycols having two OH end groups and the molecular weights of 1000 and 3205 (g/mole) are used, and the molecular structure is represented by the following: ##STR1## wherein R is an alkyl, aryl or arylalkyl group. 
     1 mole of long chain polysilicone polyglycol with the molecular weight of 1,000 and 3,205 (g/mole) together with 2 moles of isophorone diisocyanate are added into the reaction tank to be thoroughly mixed by stirring. Then 0.08 g of dibutyltin dilaurate is added and mixed uniformly. The mixture is heated to 50° C., reacted by stirring at 50° C. for 4 hours and polymeric co-catalyst Nos. IS1000-2 and IS3205-2 are obtained respectively. 
     0.5 mole of long chain polysilicone polyglycol with the molecular weight of 1000 is well mixed with 0.5 mole of polypropylene oxide long chain polyether polyglycol with the molecular weight of 1000. Thereafter, the mixture together with 2 moles of isophorone diisocyanate is poured into the reaction tank to be thoroughly stirred. Then 0.08 g of dibutyltin dilaurate is added and mixed uniformly. The resulting mixture is heated to 50° C. for 6 hours and polymeric co-catalyst No. IPS1000-2 is obtained. 
     The Preparation of Active Caprolactam Sodium Salt Catalyst Composition 
     After dehydrated and purified caprolactam monomer with low moisture content less than 500 ppm, is heated to 90° C., proper amount (as shown in Table 5.1) of sodium hydride is added and stirred to an form active caprolactam sodium salt catalyst composition. Thereafter, the catalyst composition is placed in the active caprolactam sodium salt catalyst composition tank with nitrogen gas and held at a temperature of 90°-110° C. 
     The Preparation of Polymeric Co-Catalyst Composition 
     Dehydrated and purified caprolactam monomer with low moisture content, less than 500 ppm, together with polymeric co-catalyst (the types and amounts as shown in Table 5.1) are added into polymeric co-catalyst composition tank with nitrogen gas and heated to a temperature of 90°-110° C. 
     The Pultrusion Processing of Long Fiber-Reinforced Anionic Polymerization Nylon Composites 
     The glass long fiber-reinforced nylon composites with the pulling rate of 35 to 40 cm/min (mold length: 1 m) are obtained by means of the same pultrusion processing method of nylon composites as shown in FIG. 2.1 using PPG Co. #247 glass roving as reinforced long fiber and the formulation of nylon matrix as shown in Table 3.1 under the reaction conditions in Table 5.1. In this example, the mechanical properties of the products of glass long fiber-reinforced nylon composites manufactured by pultrusion processing are tested and listed as shown in Table 5.1. 
     
                       TABLE 5.1                                                   
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Finished product                                                          
               IPS1000-2 IS1000-2  IS3205-2                               
number                                                                    
10-G76                                                                    
10-G75                                                                    
10-G75                                                                    
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Polymeric co-catalyst                                                     
               IPS1000-2 ISI1000-2 IS3205-2                               
number                                                                    
NaH amount (g/1 Kg re-                                                    
               02.5      0.25      0.3                                    
action mixture)                                                           
Temperature of reaction                                                   
mixture (°C.)                                                      
               105       105       105                                    
Viscosity of reaction mix-                                                
                55        35        45                                    
ture (cps)                                                                
Weight fraction of                                                        
                10        10        10                                    
polymeric co-catalyst in                                                  
the nylon matrix (%)                                                      
Mechanical properties:                                                    
Type of re-enforced long                                                  
               Glass fiber                                                
                         Glass fiber                                      
                                   Glass fiber                            
fiber                                                                     
Content of fiber (weight                                                  
               75.6      74.7      75.2                                   
%)                                                                        
Tensile modulus (MPa)                                                     
               44150     42950     43150                                  
Tensile strength (MPa)                                                    
               1090      930       970                                    
Heat distortion                                                           
               200       198       200                                    
temperature (°C., 264 psi)                                         
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