CN102432929A - Improved polymer vulcanized rubber and preparation method thereof - Google Patents
Improved polymer vulcanized rubber and preparation method thereof Download PDFInfo
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- CN102432929A CN102432929A CN2011102783708A CN201110278370A CN102432929A CN 102432929 A CN102432929 A CN 102432929A CN 2011102783708 A CN2011102783708 A CN 2011102783708A CN 201110278370 A CN201110278370 A CN 201110278370A CN 102432929 A CN102432929 A CN 102432929A
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Abstract
The invention discloses a polymer composition comprising (i) a polymer derived from a main polymer chain of monomers of (ia) a first monomer based on 30% to 100% of the polymer by weight, wherein at least one of secondary carbon and tertiary carbon is introduced to the main polymer chain of the first monomer, and (ib) at least one of other monomers based on 0-71% of the polymer by weight, (ii) at least one lithium salt, and (iii) at least one antioxidant. The invention also provides a method used for improving the hot-air aging and water resistance fluid characteristics of the polymer composition. The method comprises a step for mixing the polymer with at least one lithium salt and at least one antioxidant.
Description
Technical field
The present invention relates to a kind of improved polymer sulfuration rubber and relate to a kind of based on the new type of polymer composition and method of making the same.In particular, the present invention relates to have improved hot air aging property and to the nitrile polymer vulcanized rubber of the improved anti-swelling property of water medium.
Background technology
Oxidizing condition is a problem that industry faces to the influence of the vulcanized rubber that obtains from the polymkeric substance with carbon-to-carbon unsaturated double-bond always; Particularly this problem is particularly outstanding when these vulcanized rubbers are exposed in the higher temperature for a long time, and this area has been developed several different methods and attempted to address this problem.
The carbon-to-carbon double bond of the known this polymkeric substance of people has started to be attacked the oxidation of this vulcanized rubber; A kind of scheme of dealing with problems that problem is attacked in oxidation be to use seldom or the polymkeric substance that does not have carbon-to-carbon double bond; This polymkeric substance comprises the butyl rubber of the carbon-to-carbon unsaturated double-bond that typically contains 0.5～3.0 molar percentage of having an appointment, and does not perhaps comprise the ethylene-propylene copolymer of unsaturated link(age).
In some concrete application, like different flexible pipes and the sealing member in automobile engine compartment, require to have combine oil-proofness and in long-time under comparatively high temps the aggressive sulfide polymer of aerial antioxidant.Conjugated diolefine and α, the vulcanized rubber of the multipolymer of alpha, beta-unsaturated nitriles like acrylonitrile butadiene copolymer, is commonly called paracril (NBR), because their oil-proofness is well-known.Yet therefore the carbon-to-carbon unsaturated double-bond that they comprised also is vulnerable to oxidation and attacks, only if in order to produce oxidation resistant vulcanized rubber special batching program is set.
For the quantity that reduces carbon-to-carbon unsaturated double-bond among the NBR and keep the oil-proofness of this multipolymer simultaneously, thereby developed that a lot of methods are come the carbon-to-carbon unsaturated double-bond of hydrogenated nbr selectively and these nitrile groups of not hydrogenation produce hydrogenant NBR or HNBR.This hydrogenization is for example at GB1, discloses in 558,491, and its content mode is by reference incorporated this paper into.
Although the development of HNBR is a major progress in this area, still there is very big room for improvement in it.
U.S. Pat-A-6,214,922 have proved successfully that the Combination application of inhibitor and alkali can improve the hot air aging property of hydrogenant nitrile vulcanized rubber significantly.
U.S. Pat 2002/072557A1 has also disclosed the inhibitor based on the organic polymer of the salt of the sterically hindered phenolic compound with at least two phenolic hydroxyl group groups.
Yet, though at US-A-6,214; It is very useful that the vulcanized rubber of mentioning in 922 is used for high temperature, but works as at US-A-6 214; Vulcanized rubber of mentioning in 922 and aqueous medium; When especially contacting with water, can observe high swelling phenomenon, this has just limited yellow soda ash and under the situation of aqueous medium or water vapour existence, has been used for the application under the comparatively high temps.Further, exist a kind of needs exploitation to have improved physical properties, for example hot air aging property has polarizable medium, for example the polymer sulfuration rubber of the anti-swelling property of water and aqueous medium.
Summary of the invention
An object of the present invention is to avoid or reduce the above-mentioned shortcoming that exists in the prior art.
Another object of the present invention provides a kind of new type of polymer vulcanized rubber.
A further object of the present invention provides a kind of a kind of method that is used to make said new polymers vulcanized rubber.
A further object of the present invention provides a kind of new polymer compsn that is used to make polymer sulfuration rubber.
A further object of the present invention provides and is used to improve the hot air aging property of polymer sulfuration rubber and improves a kind of method to the anti-swelling property of polarizable medium simultaneously.
Therefore, in view of one of above purpose, the present invention has disclosed a kind of polymer compsn, comprises:
(i) has polymkeric substance derived from following monomeric host polymer chain
(ia) based on first monomer of this polymkeric substance at least 30% weight ratio to 100% weight ratio, this first monomer introduce in secondary carbon and the tertiary carbon at least one to this host polymer chain and
(ib) based on this polymkeric substance at least a other monomers from 0～70% weight ratio;
(ii) at least a lithium salts; And
(iii) at least a inhibitor.
A kind of preferred polymeric compositions comprises:
(i) hydrogenant nitrile polymer;
(ii) at least a lithium salts;
(iii) at least a inhibitor;
(iv) at least a weighting agent;
(v) curing system; And
(vi) optional at least a carbodiimide, at least a carbodiimide or their mixture of gathering.
On the other hand, the invention provides a kind of method that is used to make polymer sulfuration rubber, this method comprises carries out the sulfurized step with polymer compsn, and this polymer compsn comprises:
(i) has polymkeric substance derived from following monomeric host polymer chain
(ia) based on first monomer of this polymkeric substance at least 30% weight ratio to 100% weight ratio, at least one in this first monomer introducing secondary carbon and the tertiary carbon mentioned to this host polymer chain
(ib) based on this polymkeric substance at least a other monomers from 0～70% weight ratio;
(ii) at least a lithium salts; And
(iv) at least a inhibitor, and
(v) curing system.
On the other hand, the invention provides a kind of vulcanizable compsn, comprising:
(i) has polymkeric substance derived from following monomeric host polymer chain
(ia) based on first monomer of this polymkeric substance at least 30% weight ratio to 100% weight ratio, this first monomer is introduced in secondary carbon and the tertiary carbon at least one to this host polymer chain, and
(ib) based on this polymkeric substance at least a other monomers from 0～71% weight ratio;
(ii) at least a lithium salts; And
(iii) at least a inhibitor, and curing system.
On the one hand, the invention provides the hot air aging property and the water-proof a kind of method that are used to improve polymkeric substance again, this polymkeric substance has derived from a following monomeric host polymer chain
(ia) based on first monomer of this polymkeric substance at least 30% weight ratio to 100% weight ratio, this first monomer is introduced in secondary carbon and the tertiary carbon at least one to this host polymer chain, and
(ib) based on this polymkeric substance at least a other monomers from 0～71% weight ratio;
Comprise said polymkeric substance and at least a lithium salts and at least a inhibitor are carried out the blended step.
Again on the one hand; The invention provides a kind of polymer sulfuration rubber; This vulcanized rubber has makes at least 50% of its original broken elongation keep the hot air aging time at least about 500 hours under 170 ℃; And have the swelling characteristic that in aqueous medium, diverted via, this vulcanized rubber is derived from the curing system that with the superoxide is the basis.
At this point; We have found that; Compared with prior art; In polymer sulfuration rubber, add inhibitor and lithium salts and carbodiimide or gather carbodiimide or the particular combination of their mixture randomly, can make that the hot air aging property of this vulcanized rubber is improved significantly, promptly; The tolerance of in air, oxidation being attacked when under oxidizing condition, under higher temperature, wearing out is improved and improves, and valuable can also being improved significantly the anti-swelling property of aqueous medium simultaneously.
Aqueous medium described in the present invention is meant the mixture of water, water vapour or water and other polarizable mediums (like glycols, polyethylene glycols).Vulcanized rubber of the present invention for aqueous medium and simultaneously with system that fuel and/or oil contacts in application particularly suitable, this is fine because of this vulcanized rubber tolerance and oil resistant/fuel property to swelling in aqueous medium.Such decorum typically is used in the coolant loop of automobile.Therefore vulcanized rubber of the present invention be used at least contact with aqueous medium on one side the other side also the application in the anti-fuel of needs and/or the oily system be very useful, the fluid circuit in automobile for example.Vulcanized rubber of the present invention can prove with a lot of modes with improving in the hot air aging characteristic and to the anti-swelling property of aqueous medium; For instance, comprise in the following areas improvement: (i) need this vulcanized rubber under 170 ℃, to keep time of at least 50% of its original 100% elongation at break; (ii) drop to the original broken elongation below 50% before in one specified period this vulcanized rubber can be exposed in its maximum operation (service) temperature; And (iii) when comparing with the vulcanized rubber that does not have additive to process, volume and/or the quality change of limit exposure behind water and/or aqueous medium consumingly.The additive of indication is meant inhibitor and lithium salts and randomly at least a carbodiimide, at least a combination that gathers carbodiimide or their mixture in the present invention.The characteristic of vulcanized rubber of the present invention can also be in the following characteristic one or multinomial in improvement; That is, compare with the vulcanized rubber of this Additive Production not: aging after heat fluid ageing, aging back compression set, aging back dynamic elastic modulus, aging back be viscous modulus, aging back static modulus, the organic aging back of cryogenic properties, aging back hardness dynamically.
State a kind of of many aspects above that, the invention provides a kind of polymer compsn, comprise:
(i) has polymkeric substance derived from following monomeric host polymer chain
(ia) based on first monomer of this polymkeric substance at least 30% weight ratio to 100% weight ratio, this first monomer is introduced in secondary carbon and the tertiary carbon at least one to this host polymer chain, and
(ib) based on this polymkeric substance at least a other monomers from 0～71% weight ratio;
(ii) at least a lithium salts; And
(iii) at least a inhibitor.
First component of polymer compsn of the present invention is a kind of polymkeric substance; It is: (i) have derived from a following monomeric host polymer chain: (ia) based on first monomer of this polymkeric substance at least 30% weight ratio to 100% weight ratio; This first monomer is introduced in secondary carbon and the tertiary carbon at least one to this host polymer chain, and (ib) based on this polymkeric substance at least a other monomers from 0～70% weight ratio.
In this manual, term " polymer " " be meant to have a more wide in range implication, be intended to comprise polymkeric substance with a host polymer chain, this host polymer chain comprises at least one secondary or tertiary carbon.It is to have two Wasserstoffatomss and its key bonded carbon atom that those skilled in the art know secondary carbon, and tertiary carbon is to have a Wasserstoffatoms and its key bonded carbon atom.This polymkeric substance can be homopolymer, multipolymer, terpolymer or its analogue.And can be the mixture of multiple polymers, and being at least a polymkeric substance in this mixture, its prerequisite has the main chain character of this polymkeric substance of above description.
The polymkeric substance that is suitable in this use can be a kind of elastomerics, and hydrocarbon rubbers for example has at least one ethene and be unsaturated link(age) and through this unsaturated link(age) and polymerisable a plurality of monomeric a kind of graft copolymer or segmented copolymer, with and analogue.
Elastomerics is well-known to those skilled in the art; The elastomerics that is fit to can be selected from by tree elastomer (NR), cis-1 cohort that 4-polyisoprene rubber (IR), polybutadiene rubber (BR), SBR styrene butadiene rubbers (SBR), paracril such as acrylonitrile-butadiene rubber (NBR), hydrogenant acrylonitrile-butadiene rubber (HNBR), ethylene-propylene monomer rubber (EPM), ethylene-propylene-diolefinic monomer rubber (EPDM), ethylene-vinylacetate rubber (EVM) and analogue are formed for instance.Certainly, it is precondition with the consistency, can use two kinds or more any aforesaid mixture of polymers at this.
Preferably, the polymkeric substance that is used for polymer compsn of the present invention is a kind of elastomerics.More preferably; This elastomerics is to be selected from a kind of nitrile polymer, ethylene-propylene copolymer, ethylene-propylene-non-conjugated diene trimer, vinyl-vinyl acetate copolymer (for example the trade name of Lanxess Deutschland GmbH is the EVM of Levapren and Levamelt), the cohort that vinylbenzene/conjugated diene copolymer, hydrogenant vinylbenzene/conjugated diene copolymer, TR 301, tree elastomer, polyhutadiene and their mixture are formed.
" nitrile polymer " of indication is meant the multipolymer that comprises a kind of conjugated diolefine and a kind of unsaturated nitrile in this manual.
This conjugated diolefine can be the conjugated diolefine of a kind of C4-C6.For example can be selected from by divinyl, isoprene, 1,3-pentadiene, 2 group that 3-dimethylbutadiene and their mixture are formed.Preferred C4-C6 conjugated diolefine is a divinyl.
This unsaturated nitrile can be the α of a kind of C3-C5, and alpha, beta-unsaturated nitriles for example is selected from the group that is made up of vinyl cyanide, methacrylonitrile, ethyl acrylonitrile and their mixture.The α of preferred C3-C5, alpha, beta-unsaturated nitriles is a vinyl cyanide.
Preferably, this nitrile polymer is that to be selected from by hydrogenant nitrile/conjugated diene copolymer, nitrile/conjugated diene copolymer, nitrile/conjugated diolefine/ethene be that undersaturated monomer trimer and hydrogenant nitrile/conjugated diolefine/ethene are the group that undersaturated monomer trimer is formed.Most preferably, this nitrile polymers is hydrogenant nitrile/conjugated diene copolymer.
Preferably, this multipolymer comprises the unsaturated nitrile of key knot of conjugated diolefine and this multipolymer weight percent 15～60 of key knot of the weight percent 40～85 of this multipolymer.More preferably, this multipolymer comprises the unsaturated nitrile of key knot of conjugated diolefine and this multipolymer weight percent 25～40 of key knot of the weight percent 60～75 of this multipolymer.Most preferably, this multipolymer comprises the unsaturated nitrile of key knot of conjugated diolefine and this multipolymer weight percent 30～40 of key knot of the weight percent 60～70 of this multipolymer.
Randomly, this multipolymer can also comprise a kind of unsaturated carboxylic acid of key knot further.This unsaturated carboxylic acid for example can be selected from the group that is made up of fumaric acid, toxilic acid, vinylformic acid, methylacrylic acid and their mixture.The amount that the unsaturated carboxylic acid of this key knot can exist is the weight percent 1～10 of common multipolymer, replaces this conjugated diene to measure accordingly with this amount.
Further, the 3rd monomer can be used in the production of this nitrile polymers.Preferably, the 3rd monomer is a kind of undersaturated single or two-carboxylic acid or derivatives thereof, for example ester class.Though the present invention can use undersaturated nitrile polymer whole or part, a useful preferable nitrile polymer is hydrogenant or partially hydrogenated nitrile polymer (HNBR) in the production of vulcanized rubber of the present invention.Preferably; This multipolymer is hydrogenant (hydrogenant nitrile/conjugated diene copolymer) and comprises remaining carbon-to-carbon unsaturated double-bond less than 30 molar percentages; More preferably 30～0.05 molar percentages; More preferably 15～0.05 molar percentages, even more preferably 10.0～0.05 molar percentages are most preferably from 5.5～0.05 molar percentages.
Second component of polymer compsn of the present invention be at least a lithium salts (ii), be preferably a kind of faintly acid lithium salts, be preferably and have at least 9.0 pk
A,More preferably 10.0, most preferably be in 10.0～14.0 scopes.
Weak acid class useful in the production process of above-mentioned lithium salts for example can be selected from the group that is made up of carbonic acid, C1-C50 lipid acid, YD 30, phosphoric acid and their mixture.Preferably, this weak acid is to be selected from carbonic acid and C1-C30 lipid acid.Being used for the most preferred salt of polymer compsn of the present invention is Quilonum Retard.
Preferably, this lithium salts is to be present in this polymer compsn from 0.5～30 part amount by weight, is preferably 1～20 part, more preferably 2.5 parts～9 parts.
The 3rd component of polymer compsn of the present invention is at least a inhibitor.The inhibitor that is fit to is well known to those of ordinary skill in the art, and preferred anti-oxidants is to be selected from the group that is made up of amine antioxidants and phenol antioxidant.More electedly, this inhibitor is diphenylamine and the sterically hindered amine that is selected from alkylating and/or arylation.Most preferably, this inhibitor is to be selected from by 4,4-is two-and the pentanoic (SDPA) and 2,2 of (1, the 1-dimethyl benzyl)-pentanoic (CDPA), styrenated, 4-trimethylammonium-1, the group that the 2-EEDQ is formed.
Preferably, the amount that in this polymer compsn, exists of this inhibitor is that per hundred parts of weight polymers contain 0.5～4 weight part.
In the above-mentioned polymer compsn of setting forth among the present invention, use the combination of lithium salts and inhibitor, can obtain having the polymer sulfuration rubber of improved hot air aging property combination the improved anti-swelling property of aqueous medium.The best of breed of lithium salts and inhibitor is the combination of Quilonum Retard and CDPA or SDPA.
Most preferred, compsn of the present invention comprises hydrogenant nitrile/conjugated diene copolymer as a kind of polymkeric substance, and Quilonum Retard and CDPA are as inhibitor.
Randomly, polymer compsn of the present invention further comprises at least a carbodiimide, at least a carbodiimide or their mixture of gathering.Preferred carbodiimide is commercially available commodity Rhenogram P50 by name.This composition can be 0～15 weight part, preferred 0～10 weight part, and most preferably the amount of 0～2 weight part is used in polymer compsn of the present invention.
Preferably further comprise a kind of weighting agent (iv) according to polymer compsn of the present invention.The character of this weighting agent is not to receive that especially restriction and the weighting agent that is fit to are that those skilled in the art can select.For example carbon black, clay, titanium oxide, silicon and analogue thereof.The amount of weighting agent is conventional.Preferably, the amount that weighting agent exists is in hundred parts of parts by weight polymer, contains the weighting agent of 20～130 weight parts, and better is 20～100 weight parts, and the best is 40～80 weight parts.
Preferably, polymer compsn of the present invention further comprises a kind of curing system (iii), and the curing system that is fit to is conventional selection the well-known to those skilled in the art.
In one embodiment, the curing system of the present invention's use comprises a kind of organo-peroxide, for example Di Cumyl Peroxide 99.Preferably, these curing systems based on sulphur further comprise for example ZPO of a kind of superoxide.
In another embodiment, the used curing system of the present invention comprises reactive phenolic resin and lewis acid acvator.Reactive phenolic resin can react through the formaldehyde with an a pair of substituted phenol and a molar excess and prepare, can be referring to U.S. Pat 2,726,224, and its content mode is by reference incorporated this paper into.It is well-known using these resol at the curing system that is used for butyl rubber.
The reactive phenolic resin that preferably contains at least 3 weight parts in per hundred parts of weight nitrile polymers according to the curing system that uses in the method for the present invention.More preferably use by this reactive phenolic resin that contains 8～16 weight parts in per hundred parts by weight polymer.
This lewis acid acvator can be used as an independent component and exists, for example tin protochloride (SnCl2) or sovprene.Alternately, this lewis acid acvator may reside in the structure of this resin itself, for example the alkyl phenolic resin of bromomethylation.The purposes that is used for these halogenated resins of butyl rubber in these curing systems is well-known to those skilled in the art.
The present invention further relates to a kind of method that is used for production polymer sulfuration rubber, and this method comprises carries out the sulfurized step with the polymer compsn of the present invention that comprises a kind of curing system.Polymer compsn that is fit to and curing system are as stated.A preferred polymeric compositions comprises:
(i) hydrogenant nitrile polymer;
(ii) at least a lithium salts;
(iii) at least a inhibitor;
(iv) at least a weighting agent;
(v) curing system; And
(vi) randomly at least a carbodiimide, at least a carbodiimide or their mixture of gathering.
In the method for the invention, this polymkeric substance, lithium salts, inhibitor and randomly aforesaid other components and this curing system can mix with the mode of any routine well known by persons skilled in the art.For example can on roller rubber mixing mill or Banbury mixer, mix.Therefore, to mix and during mixing keep its temperature with a kind of mode of routine be known in those skilled in the art to this polymer compsn.
According to a preferred embodiment that is used for preparing the method for polymer compsn of the present invention; Prepare a masterbatch in the first step; This is through mixing (ii) and randomly other food ingredients of a kind of polymkeric substance (i), at least a lithium salts; Preferred at least a weighting agent, for example carbon black, clay, titanium oxide or silicon, particularly silicon.Based on the gross weight of masterbatch, this masterbatch typically comprises 30～70% weight, this polymkeric substance (i) and 70～30% weight of preferred 40～60% weight, and at least a lithium salts of preferred 60～40% weight is (ii).Based on the gross weight of this masterbatch, randomly other food ingredients, particularly silicon up to 10% weight can be used for preparing this masterbatch, replace a corresponding amount of this polymkeric substance (i) by it.
In the method according to the invention, preferably use this polymer compsn of ordinary method heating well known in the art to form vulcanized rubber.Preferably, this polymer compsn is heated in 130 ℃～200 ℃ scopes, more preferably from 140 ℃～190 ℃, more preferably from 150 ℃～180 ℃, most preferably need heat 5 minutes to 30 minutes.
Other conventional food ingredients can mix with this multipolymer through the mode of routine, and other batchings comprise acvator, like zinc oxide and Natural manganese dioxide, softening agent, processing aid, toughener, weighting agent, promotor and retarding agent etc.
In another embodiment, a kind of polymer sulfuration rubber of producing of the above-mentioned method of mentioning of this specification sheets.Preferably; This polymer sulfuration rubber has makes at least 50% of its original broken elongation keep at least about 500 hours hot air aging time under 170 ℃; And have improved swelling characteristic in aqueous medium, this vulcanized rubber is derived from a kind of curing system based on superoxide.Preferably, this aqueous medium is selected from the mixture of water or water/glycol.
In another embodiment, the present invention has disclosed a kind of be used to improve the hot air aging property of polymkeric substance and the method for water tolerance fluid characteristics, and this polymkeric substance has derived from following monomeric a kind of host polymer chain
(ia) based on first monomer of this polymkeric substance at least 30% weight ratio to 100% weight ratio, this first monomer is introduced in secondary carbon and the tertiary carbon at least one to this host polymer chain, and
(ib) based on this polymkeric substance at least a other monomers from 0～70% weight ratio;
Comprise said polymkeric substance and at least a lithium salts and at least a inhibitor are carried out the blended step.
Embodiment
In following each embodiment, used material is following:
Therban A 3470: a kind of hydrogenant nitrile butadiene polymer, Lanxess Deutschland GmbH is commercially available;
Corax N 550/30: carbon black, FEF Evonik-Degussa AG are commercially available;
Zinkoxyd Aktiv: acvator, sedimentary zinc oxide fine granular, Lanxess Deutschland GmbH is commercially available;
Maglite DE: Natural manganese dioxide, acvator, CP Hall is commercially available;
Luvomaxx CDPA: Lehmann & Voss is commercially available;
Dynamar RC-5251Q: yellow soda ash, Dyneno is commercially available;
Edenor C 1898-100: tensio-active agent, Cognis GmbH is commercially available;
TAIC: powder type, with triallyl isocyanurate (TAIC) goods of very fine silicon as carrier, Kettlitz-Chemie GmbH & Co.KG is commercially available;
Perkadox BC-40 B-PD: two (three grades-butyl peroxy sec.-propyl)-benzene, particulate state, Akzo Noble AG is commercially available.
Embodiment 1-10
Following program is used to each among ten embodiment.The polymer compsn that in embodiment 1-10, uses is shown in 1.Use routine techniques in mixing roll, to mix, and vulcanized 20 minutes down at 180 ℃.
Tensile stress (tensile strength) when measuring the vulcanized rubber fracture according to ASTM-D412-80.Confirm the hot air aging character of vulcanized rubber according to ASTM-D573-88, use Shore scleroscope to measure hardness, shown in table 2-6 according to ASTM-D2240-81.
Shown in table 1-7; The character of HNBR vulcanized rubber has been described; When the vulcanized rubber with embodiment 1 and 2 (only using conventional Natural manganese dioxide additive or Quilonum Retard) compares, the meliority of hot air aging property and the showing of improved aqueous medium swelling property of the vulcanized rubber of embodiment 3-6 (using additive according to the invention).
Table 1:HNBR vulcanized rubber formula table
The physicals test result of the not aged HNBR vulcanized rubber of table 2
The physicals of the HNBR vulcanized rubber after 170 ℃ of following 168h of table 3
The physicals of the HNBR vulcanized rubber after 170 ℃ of following 336h of table 4
The physicals of the HNBR vulcanized rubber after 170 ℃ of following 504h of table 5
Table 6 HNBR vulcanized rubber compressive set under 160 ℃ in warm air
The physicals of table 7 100 ℃ of following 24h HNBR vulcanized rubber afterwards in water
Claims (10)
1. polymer compsn comprises:
(i) has a kind of polymkeric substance derived from following monomeric host polymer chain
(ia) based on first monomer of at least 30% weight～100% weight of this polymkeric substance, this first monomer is introduced in secondary carbon and the tertiary carbon at least one to this host polymer chain, and
(ib) based at least a other monomers in this polymkeric substance 0～70% weight range;
(ii) at least a lithium salts; And
(iii) at least a inhibitor.
2. the described photosensitive resin compsn of claim 1; Wherein this polymkeric substance is a kind of elastomerics, and it is selected from the group that is made up of nitrile polymer, ethylene-propylene copolymer, ethylene-propylene-non-conjugated diene trimer, ethylene-ethyl acetate copolymer, vinylbenzene/conjugated diene copolymer, hydrogenant vinylbenzene/conjugated diene copolymer, TR 301, tree elastomer, polyhutadiene and their mixture.
3. the described polymer compsn of claim 2, wherein this nitrile polymer is selected from by hydrogenant nitrile/conjugated diene copolymer, nitrile/conjugated diene copolymer, nitrile/conjugated diolefine/ethylene unsaturated monomers trimer and group that hydrogenant nitrile/conjugated diolefine/the ethylene unsaturated monomers trimer is formed.
4. the described polymer compsn of claim 3, wherein said hydrogenant nitrile/conjugated diene copolymer comprises the participation carbon carbon unsaturated link(age) less than 30 molar percentages.
5. each described polymer compsn of claim 1-4; Wherein this lithium salts is a kind of faintly acid lithium salts; Have at least 9.0 pka, this weak acid is selected from carbonic acid or C1-C30 lipid acid, and the amount that lithium salts exists is to contain 0.5～30 weight part in per hundred parts of these polymkeric substance of weight; Inhibitor is a kind of amine or phenol antioxidant, and the amount that this inhibitor exists is to contain 0.5～4 weight part in per hundred parts of these polymkeric substance of weight.
6. the described polymer compsn of claim 5, wherein lithium salts can be Quilonum Retard.
7. each described polymer compsn of claim 1-6 further comprises at least a carbodiimide, at least a carbodiimide or their mixture of gathering.
8. polymer compsn comprises:
(i) hydrogenant nitrile polymer;
(ii) at least a lithium salts;
(iii) at least a inhibitor;
(iv) at least a weighting agent;
(v) curing system;
(vi) optional at least a carbodiimide, at least a carbodiimide or their mixture of gathering.
9. a method of making polymer sulfuration rubber comprises the described polymer compsn of claim 8 is carried out the sulfurized step.
10. hot air aging property and fluidic method of water tolerance that is used to improve polymkeric substance, this polymkeric substance has derived from following monomeric a kind of main polymeric chain:
(ia) based on first monomer of at least 30% weight～100% weight of this polymkeric substance, this first monomer is introduced in secondary carbon and the tertiary carbon at least one to this host polymer chain, and
(ib) based at least a other monomers in this polymkeric substance 0～70% weight range;
Comprise said polymkeric substance and at least a lithium salts and at least a inhibitor are carried out the blended step.
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| CN111316021A (en) * | 2017-11-07 | 2020-06-19 | Nok株式会社 | Gasket material |
| WO2020175151A1 (en) * | 2019-02-27 | 2020-09-03 | Nok株式会社 | Hydrogenated nbr composition |
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| CN101445664A (en) * | 2007-11-30 | 2009-06-03 | 朗盛德国有限责任公司 | Improved polymer vulcanizate and process for the production thereof |
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| CN101445664A (en) * | 2007-11-30 | 2009-06-03 | 朗盛德国有限责任公司 | Improved polymer vulcanizate and process for the production thereof |
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