Halogenated butyl rubber of improved scorch characteristics
United States Patent Feniak Apr. 29, 1975 HALOGENATED BUTYL RUBBER OF 3.190.865 6/1965 Miller 260/2317 H IMPROVED SCORCH CHARACTERISTICS 3.255 l54 6/1966 Dudley 260/782 3,458,46l 7/1969 Mihal 260/23.7 H Inventor: George Femak, y g Ontario. $534,123 10/1970 Bostock er al. zoo/23.7 H  
 Canada OTHER PUBLICATIONS [73] Assignee: Polysar Limited, Sarhia, Ontario,  
 C d Cowan, J. Amer. Oil Chemists Soc., 39, 534-545 1962 [22] Filed: Oct. 23, 1973 1 PP 408542 Primary Examiner-Murray Tillman Assistant Examiner-Arthur H. Koeckert [30] Foreign Application Priority Data Attorney, Agent, or F irm-Stevens, Davis, Miller &amp;  
 Nov. 24, 1972 Canada 157388 Moshe [52] US. Cl 260/85.3 H; 260/5; 260/318 DR; [57] ABSTRACT 260/336 AQ; 260/888; 260/890 [51 Int. Cl. C08d 9/04; C080 1 1/34 The scorch charactensucs of halogenated butyl rubber [58] Field of Search&#34;. 260/23] H 853 H 23] M compounds are improved by the addition of one of or i 260/782 :1 mixture of the free acid or the magnesium, aluminum, calcium or barium salts of oligomers of linoleic [56] References Cited 2,958,667 ll/I960 Eby ct ul 260/217 H HALOGENATED BUTYL RUBBER OF IMPROVED SCORCH CHARACTERISTICS This invention relates to the stabilization of halogenated butyl rubber against premature cross-linking during compounding.  
  Halogenated butyl rubbers are fast curing and, as a result, their compounds tend to be susceptible to premature vulcanization when part or all of the curing ingredients are present and before all of the fabrication and shaping stages have been completed. When such premature vulcanization takes place, the compounds become tough and unworkable. Premature vulcanization is commonly referred to as scorchingg. The problem can be reduced by the use of certain scorch retarders. However, up to the present, the known scorch retarders are not entirely satisfactory in providing adequate time for processing or compounding in the production of the final shaped articles.  
  It is an objective of this invention to provide vulcanizable halogenated butyl compounds having improved scorch characteristics.  
  It has now been discovered that vulcanizable compositions comprising halogenated butyl have longer scorch times when a scorch retardingagent selected from at least one of the free acid and the magnesium, aluminum, calcium or barium salts of an oligomer of linoleic acid is incorporated into the composition.  
  The term butyl rubber as employed herein is intended to refer essentially to a vulcanizable rubbery copolymer containing from about 85 to 99.5% combined isoolefm having from 4 to 8 carbon atoms and 0.5 to 15% combined conjugated diolefin having from 4 to 8 carbon atoms. Such copolymers and their preparation are well known in the industry. The isoolefin, such as isobutylene, is mixed with a conjugated diolefin, such as butadiene or isoprene, and an inert diluent selected from C4 to C aliphatic alkenes and chlorinated hydrocarbons such as methyl chloride, ethyl chloride, methylene chloride and ethylene dichloride. The monomers may form from 10 to 50% by weight of the total monomer/diluent mixture. The mixture is polymerized in a reactor at a temperature in the range from about to about 165C using cationic catalysts well known in the art. The polymerization reaction proceeds rapidly to produce a copolymer in the form of a slurry in the diluent.  
  The preferred copolymer which is used to produce the halogenated butyl rubber of this invention is a copolymer is isobutylene and isoprene, preferably having an isobutylene content of from 97 to 99.5 weight per cent, most preferably from 98 to 99 weight per cent, and an isoprene content of from 0.5 to 3 weight per cent, most preferably from 1 to 2 weight per cent. The halogenated butyl rubber contains chlorine or bromine in an amount from about 0.5 to about 15 weight per cent. It contains not more than one atom of chlorine or not more than three atoms of bromine per double bond present in the original copolymer and preferably it contains from 0.5 to 2 weight per cent of chlorine or from 0.5 to weight per cent bromine. Most preferably the halogenated polymer is a brominated butyl rubber containing from 1.5 to 2.5 weight percent bromine. The butyl rubber may be halogenated by means well known in the art. The solid rubber may be reacted on a hot rubber mill with a compound which releases halogen such as nitrogen halo-succinimide and nitrogen halohydantoin. Alternatively, the butyl rubber may be dissolved in an inert hydrocarbon solvent such as pentane, hexane 0r cyclohexane and halogenated by addition to the solution of elemental chlorine or bromine and the halogenated butyl recovered therefrom.  
  Halogenated butyl rubbers may be used in various applications where rubbers are generally used and are particularly useful in applications involving adhesion to, or covulcanization with, more highly unsaturated rubbers such as natural rubber and synthetic unsaturated rubbers selected from polyisoprene, polybutadiene, styrene-butadiene polymers and ethylenepropylene-diene polymers.  
  The scorch retarding agent used in this invention is at least one of the free acid or the magnesium, aluminum, calcium and barium salts of an oligomer of linoleic acid. Linoleic acid is an organic monocarboxylic acid compound containing two carbon-carbon double bonds. lt is well known in the art that this compound will undergo oligomerization particularly to form the dimer and the trimer. Such oligomerization is achieved by the action of heat, optionally in the presence of a catalyst, to yield a compound thought to be, for the dimer, a tetra-substituted cyclohexene having two carboxyl groups and one carbon-carbon double bond external to the cyclohexene ring. Preferred oligomers of linoleic acid are the dimer and the trimer. Salts of the dimeric or trimeric acid may be readily formed such as by reacting the acid with aqueous potassium or sodium hydroxide to yield a water soluble compound which may then be reacted with an aqueous solution of, for example, calcium chloride to yield the corresponding calcium salt.  
  The quantity of scorch retarding agent required to give the degree of scorch retardation desired will depend on the type and amount of other materials present in the vulcanizable composition. Generally, the quantity of scorch retarding agent is in the range of from about 0.5 parts to about 5 parts by weight per parts by weight of the polymeric component, i.e. the total quantity of rubber, in the vulcanizable composition. Preferably the amount of scorch retarding agent is from 0.75 to 2.5 parts by weight per 100 parts by weight of the polymeric component of the vulcanizable composition.  
  The vulcanizable composition of this invention may contain, in addition to the halogenated butyl and scorch retarding agent, other unsaturated rubbers and conventional compounding ingredients such as carbon black, other fillers, oil, wax, antioxidant, and other processing aids. Other unsaturated rubbers include natural rubber and synthetic unsaturated rubbers selected from polyisoprene, polybutadiene, styrene-butadiene polymers and ethylene-propylene-diene polymers. The polymeric component of the vulcanizable composition thereby is halogenated butyl and may optionally contain at least one of the aforesaid unsaturated rubbers. The halogenated butyl forms at least 20 per cent by weight and up to 100 per cent by weight of the polymeric component. The quantity of conventional compounding ingredients contained in the vulcanizable composition will depend on the use for the final shaped article and may be varied as well known in the art. The quantity of carbon black in the composition will generally be in the range of from 20 parts by weight to 100 parts by weight per 100 parts by weight of the polymeric components.  
  The vulcanizable composition is vulcanized, on heating for a period of time, by reaction with zinc oxide, as for compositions containing halogenated butyl as the only polymeric component, or with sulphur or sulphur compound vulcanization agents alone or in combination with zinc oxide as when the polymeric component is halogenated butyl alone or in admixture with at least one other unsaturated rubber.  
 The vulcanizable composition is produced by mixing Using 200g portion, the additive shown in Table l were incorporated, using the mill mixing procedure given above. Scorch times for the compounds and stressstrain properties of the vulcanizates, which had been vulcanized for 30 minutes at 165C, were then determined.  
  The bromobutyl used was a commercial sample containing 2.1 weight per cent of bromine and having a Mooney (ML 1 12 at 125C) of 42. The carbon black the halogenated butyl rubber with the scorch retarding u ed was a general purpose furnace black, the parafagent. The process whereby the rubber and scorch refi i oil i a petroleum oil having a specific gravity of tal&#39;ding agent are mixed y be y y State mixing of 0.88 and a Saybolt Universal viscosity of 350 seconds it may be by mixing in an aqueous phase. When the at 80F, the tackifier resin used was a product of Rohm mixing is in the dry state, dry halogenated butyl and the &amp; Haas sold under the tradename Amberol ST- 1 49 and dry retarding agent are mixed by a rubber compound 15 the alkyl phenol disulphide was a product of Pennwalt ing means such as in a Banbury material mixer or on a Chemical Corporation sold under the tradename Vulrubber mill under conditions well known in the art and c 5, Th c lci m salt of the dimer acid was prepared normally used for mixing Such halogenat d butyl u as follows: 57g of linoleic acid dimer (Empol Dimer ber with compounding ingredients. The scorch retard- Acid 1022, obtained from Emery Industries Inc.) was ing agent may be mixed with the halogenated butyl as added to a stirred solution of 10g NaOH in 500 ml of a separate step in the compounding process or may be water. The reaction mixture was stirred and heated on mixed together with other compounding ingredients. a hot plate. When the temperature had reached about When aqueous phase mixing is used, the halogenated 60C, the mixture became very viscous and was then butyl may be recovered from the halogenation reaction poured into a stirred solution of 28g of CaCl in 200 ml as a slurry in water and an aqueous solution of the of water. The resultant pale yellow slurry was stirred scorch retarding agent may be mixed with said slurry, and heated to about 80C for 15 min., collected by filthe halogenated butyl mixed with the scorch retarding tration, washed thoroughly with water and air dried. agent being recovered therefrom and dried. The product was an off-white powder. The scorch time The invention is illustrated by the following examwas determined as the time when the Mooney had inples, the scope of the invention not being limited 30 creased by 5 Mooney points above the minimum thereto. Mooney, using a test temperature of 125C and the stress-strain properties were determined using ASTM procedures. EXAMPLE 1 Comparison of the scorch times for experiments 1, 2  
  and 3 and for 4 and 5 and for 6 and 7 show that the ad- Using a Banbury mixing procedure, with the rotor dition of the calcium salt of the dimer of linoleic acid running at 77 rpm, the rotor and gates at 215F and does cause an increase in the scorch time in different steam and water to the Banbury both Off, the following recipes. The stress-strain properties show that the prescompound was mixed for a total mixing time of 5 minence of the scorch retarder does not detract from the utes, the quantities being parts by weight: properties of the vulcanizates.  
 TABLE I Calcium salt Scorch Experiment Benzothiazyl Magnesium of Dimer of Time Tensile 300% Elongation No. Disulphide Oxide Linoleic Acid t /125C Strength Modulus g g g minutes Kg/cm Kg/cm 1 (Control) 0 0 0 6.62 106 54 560 2 0 0 1.1 8.77 100 56 520 3 O 0 2.2 9.57 101 58 500 4 (Control) 0 1.1 0 7.02 100 58 500 5 0 1.1 1.1 15.33 101 43 570 6 (Control) 1.1 0 0 7.18 111 51 600 7 1.1 0 1.1 9.40 115 47 610 Bromobutyl 550 EXAMPLE 2 gfl ii&#39; fig 3 A compound identical with that of Example 1 was Carbon P j 440 prepared in a Banbury mixer. Into 1200 parts of this Parafiinic Oll l 10 Tackific, resin 29 compound was mixed, using a rubber compounding Using 1200 parts of this compound, the following ingredients were incorporated by mixing on a rubber compound mill, the temperature of the rolls being about 85F:  
 Zinc oxide 33.] parts by weight Bcnzothiazyl disulphide 3.3 Alkyl phenol disulphide 6.6  
 mill, the following:  
 Zinc oxide 32.9 parts by weight Benzothiazyl Disulphidc 6.6 Vultac 5 6.6  
 TABLE 11 Scorch Experi- Time ment t,-,/125C No. Additive Minutes 1 Nil (Control) 6.97 2 Calcium salt of dimer of&#39;linoleic acid 10.75 3 Calcium salt of trimer of linoleic acid 1 1.9 4 Barium salt of dimer of linolcic acid 12.45 5 Barium salt of trimer of linoleic acid 15.5 6 Nil (Control) 6.37 7 Dimer of linoleic acid 8.87 8 Trimer of linoleic acid 9.0 9 Magnesium salt of dimer of linoleic acid 7.4 10 Magnesium salt of trimer of linoleic acid 10.41 1 1 Aluminum salt of dimer of linoleic acid 7.06 12 Aluminum salt of trimer of linoleic acid 7.45  
 The linoleic acid dimer and trimer were commercial products available from Emergy Industries Ltd. as Empol Dimer 1022 and Empol Trimer 1040 respectively. The salts were prepared as described in Example 1.  
 EXAMPLE 3 Bromobu tyl-eontaining compounds were prepared using the ingredients in Part A of Table 111. The bromobutyl had the bromine contents and Mooney as (ML 1 12 at 125C) shown. To l00-gram portions of each compound was added one gram of the calcium salt of the dimer acid of Example 1. Scorch times were determined on these two portions and on a portion of each original compound, as controls, with the results shown in Part B of Table 111.  
 TABLE 111 PART A Experiment No. l 2 3 4 Bromobutyl 75 75 100 100 Wt. of bromine of bromobutyl 1.9 1.65 1.9 1.65 Mooney of bromobutyl 44 43.5 44 43 5 Natural Rubber 25 25 General purpose furnace carbon black 62.5 62.5 62.5 62.5 Stcaric acid 1 l l 1 Benzothiazyl disulphide 1.25 1.25 1.25 1.25 Paraffin oil 14 14 l4 l4 Tackificr resin 4 4 4 4 Dipentamethylene thiuram tetrasulphide 0.2 0.2 Zinc oxide 5 5 5 5 Sulphur 0.5 0.5 4,4&#39;-Dithiomorpholine 0.15 0.15  
 PART B Calcium salt of linolcic acid dimer 0* 1 gram 0* 1 gram Scorch time t;,/ 135C (mins.) 10.88 15.77 10.2 14.85  
 *Contml EXAMPLE 4 Using a Model B Banbury. a masterbatch was prepared of the following components, using the procedure of Example 1, all parts being parts by weight.  
 .Ethylene-propylene-ethylidene norbomene po1ymer* 160 Bromobutyl l Styrene-butadiene rubber Natural rubber 360 Fast extruding furnace carbon black 400 Stcaric acid 8 Light paraffinic oil 96 Paraffin wax 12 *Royalene 502, sold by United States Rubber Co. lnto 1200 parts of this masterbatch were blended on a cool rubber compounding mill the following:  
 Into 1200 parts of this masterbatch were blended on a cool rubber compounding mill the following:  
 Zinc oxide 22 parts Sulphur 3.7 Benzothiazyl disulphide 5.5 Vultac 5 9 This compound was divided into portions of 150g weight and to each portion was added the quantity shown in Table IV of the calcium salt of the dimer of linoleic acid and the scorch time was then determined on each sample.  
 TABLE IV Quantity of Calcium Salt Scorch Time Experiof linoleic acid dimer t 1 35C ment No. g (phr) minutes *Control The effect on the scorch time of increasing the quantity of the scorch retarding agent in the compound can clearly be seen.  
 EXAMPLE 5 Using a mill mixing procedure a vulcanizable mixture was prepared using a sample of chlorobutyl as the rubber component, the contents of the mixture being as given in Table V. The mixture was divided into two equal portions, and to one portion was added lg of the calcium salt of the dimer of linoleic acid. The scorch time was determined for each portion of the mixture.  
 The chlorobutyl used had a chlorine content of 1.1 weight per cent and a Mooney (ML 1 4 at C) of 56. The presence of the calcium salt of the linoleic acid dimer clearly increases the scorch time of the vulcanizable mixture.  
 EXAMPLE 6 A compound of bromobutyl was prepared, using a mill mixing procedure, by mixing 200g of bromobutyl, 100g of a semi-reinforcing furnace carbon black, 2g of stearic acid and, as the curing agent, 10g of zinc oxide. The bromobutyl used had a Mooney of 45 and contained l.9 weight per cent bromine. This compound served as a control. A second compound was prepared in exactly the same manner with the exception that lg of the calcium salt of the dimer of linoleic acid was added. The scorch time (t 135C) for the control compound was 10.5 minutes whereas that for the compound containing the scorch retarder of the invention was 11.7 minutes.  
 What is claimed is:  
  l. A vulcanizable composition having improved scorch characteristics which comprises a polymeric component comprising halogenated butyl rubber and a scorch retarding agent selected from at least one of the free acid and the aluminum, barium, calcium and magnesium salts of an oligomer of linoleic acid, said scorch retarding agent being present in an amount from about 0.5 parts to about 5 parts by weight per lOO parts by weight of said polymeric component.  
  2. The composition of claim 1 in which said halogenated butyl rubber is selected from chlorobutyl and bromobutyl.  
  3. The composition of claim 2 in which said halogenated butyl rubber is a polymer containing, based on hydrocarbons, from 97 to 99.5 weight per cent of isobutylene and from 0.5 to 3 weight per cent of isoprene and, based on halogenated polymer, from 0.5 to 5 weight per cent of bromine.  
  4. The composition of claim 2 in which said halogenated butyl rubber is a polymer containing, based on hydrocarbons, from 97 to 99.5 weight per cent of isobutylene, and from 0.5 to 3 weight per cent of isoprene and, based on halogenated polymer, from 0.5 to 2 weight per cent of chlorine.  
  5. The process of manufacture of an improved scorch characteristic vulcanizable composition comprising mixing a polymeric component comprising halogenated butyl rubber with from about 0.5 to about 5 parts by weight per 100 parts by weight of said polymeric component of a scorch retarding agent selected from at least one of the free acid and the aluminum, barium, calcium and magnesium salts of an oligomer of linoleic acid.  
  6. The process of claim 5 wherein said scorch retarding agent is mixed in the dry state with said polymeric component together with other compounding ingredients.  
  7. The process of claim 5 wherein said halogenated butyl rubber is mixed with said scorch retarding agent in an aqueous phase, the mixture being recovered therefrom and dried.