CN1081695A

CN1081695A - Polymer composition

Info

Publication number: CN1081695A
Application number: CN 93107590
Authority: CN
Inventors: D·R·凯尔赛; H·H·蔡
Original assignee: Shell Oil Co
Current assignee: Shell USA Inc
Priority date: 1992-05-15
Filing date: 1993-05-15
Publication date: 1994-02-09
Anticipated expiration: 2013-05-15
Also published as: AU4373193A; WO1993023448A1; CN1054615C; TW222284B

Abstract

The thermoset polymer compositions of improving shock-resistance contains 5-(3-tetrahydrobenzene-1-the yl)-metathesis polymerizable product of 2-norbornylene and the aromatic vinyl hydrocarbon compound of 2 to 10% (weight) and the segmented copolymer of a conjugation alkene or the derivative of selectionization.

Description

Polymer composition

The present invention relates to a kind of improved impact resistant composition, it contains the adducts deutero-thermoset alkene replacement polymer from 4 vinyl cyclohexene and cyclopentadiene.

It is well-known producing polymkeric substance by open loop or metathesis polymerizable ring or polycyclic olefin.Many patents and documents and materials have all related to the ring-opening polymerization effect of dicyclopentadiene in the presence of alkene displacement catalyst system.

A kind of solid-state hard not cladding polymer product of having determined application is produced in the ring-opening polymerization of dicyclopentadiene.Yet this polymerization and products obtained therefrom have many shortcomings.It is quite quantitative removing non-polymeric, otherwise just has unreacted monomer and the moulded products produced thus also will have the unpleasant odor of dicyclopentadiene in polymeric articles.

Some above-mentioned shortcoming is improved by producing alkene replacement polymer product by the adducts of 4-vinyl-tetrahydrobenzene and cyclopentadiene (providing with the dicyclopentadiene form).4 vinyl cyclohexene and cyclopentadiene are at the Diels-Alder(diels-alder) under the condition reaction generate the adducts of monomer reactant and the mixture of cyclopentadiene oligopolymer.The ring-opening polymerization result of the mixture of adducts/oligopolymer forms the hard polymerization product (referring to US-A-5095082) that does not have a dicyclopentadiene smell.

Can produce a kind of polymerization product that has more suitable character for some application by 1: 1 mole of 4 vinyl cyclohexene of ring-opening polymerization and cyclopentadiene adducts, this adducts is (referring to the WO93/02121) that segregation comes out from the mixture of above-mentioned vinyl cyclohexene and cyclopentadiene adducts and cyclopentadiene oligopolymer.This adducts mixture of 1: 1 promptly is 5-(3-tetrahydrobenzene-1-yl basically)-isomer of 2-norbornylene, can quite easily from other adducts and oligopolymer, reclaim according to a conventional method.5-(3-tetrahydrobenzene-1-yl)-and the alkene metathesis polymerizable result of 2-norbornylene forms more satisfactory and the product of may command mechanical property more, and whether in addition this part will depend in polyblend linking agent, and not essential, additional dicyclopentadiene.Although these polymkeric substance are put polymkeric substance than the alkene of dicyclopentadiene best elongation property is arranged, this polymkeric substance is still somewhat crisp thereby can not be suitable for fully possibly that this polymkeric substance stands the ballistic application scenario of hard thing.

Known the impact property (for example referring to US-A-4696985) that to improve polydicyclopentadiene by the resilient material that mixes.The gained shock strength is better, but this polymkeric substance still is not suitable for some special application.

Japanese patent application 63-92640 is described in to mix other polymkeric substance and add various resilient materials in the alkene replacement polymer of a kind of 5-(3-tetrahydrobenzene-1-base-2-norbornylene and improves shock resistance, these materials comprise polyhutadiene, polyisoprene, isoprene-isobutylene rubber, EPDM rubber and the segmented copolymer that includes styrene-butadiene-styrene and styrene-isoprene-phenylethene.In these listed elastomericss, do not distinguish the data that yet do not provide support.The evaluation of mixing these elastomericss and products obtained therefrom really shown be not whole elastomericss can both be used to improve shock resistance and add rubber ratio also be important.Some is elastomeric, and to mix its effect be to reduce the Gardner(Gardner) shock strength.In addition, mix certain other elasticity physical efficiency and improve one type shock-resistance, as notched izod intensity.A kind of 5-(3-of containing tetrahydrobenzene-1-yl can be provided)-alkene replacement polymer (it has wide improved shock-resistance) and a kind of method of improving the shock-resistance of those polymkeric substance of 2-norbornylene is favourable.

The invention provides a kind of thermoset polymer compositions, it contains 5-(3-tetrahydrobenzene-1-yl)-the metathesis polymerizable product of 2-norbornylene and according to composition total weight 2-10%(weight) a kind of impact modifying agent, it is selected from the selection hydrogenated derivatives of the elastomeric block copolymers of the elastomeric block copolymers of aromatic vinyl hydrocarbon compound and isoprene and a kind of aromatic vinyl hydrocarbon compound and conjugated alkadiene.

Composition of the present invention preferably contains the alkene metathesis polymerizable product of most 4 vinyl cyclohexene and 1: 1 adducts of cyclopentadiene.The mixture of adducts can heat 4 vinyl cyclohexene and cyclopentadiene (providing with dicyclopentadiene) down by high temperature and produce, and obtain a kind of mixture thus, it contains 1: 1 the 4 vinyl cyclohexene and the adducts of cyclopentadiene, 1: 2 adducts and 1: 3 adducts, and cyclopentadiene oligopolymer, it comprises cyclopentadiene trimer, tetramer and pentamer.The adducts mixture at high temperature particularly from 180 ℃ to 260 ℃, prepares in the inert reaction environment.Trace active material for example oxygen should be removed and inclusion within the reaction mixture of free radical scavenger also is useful.

Resulting adducts/oligomer mixture can be separated by ordinary method, and for example chromatographic separation or fractionation preferably under reduced pressure carried out.Useful especially mixture partly is 1: 1 adducts in being provided for the replacement polymer product of the present composition, mainly is 5-(3-tetrahydrobenzene-1-yl)-the 2-norbornylene.The isomeric form that this compound is represented with following molecular formula exists.

The isomer of molecular formula I a is called as " interior " isomer, and the isomer of molecular formula I b is called as " outward " isomer, to reflect the spatial relation of tetrahydrobenzene substituting group to the on-plane surface 6 joint rings of norbornylene part.The process that forms at adducts also produces the isomeric form of another kind of 1: 1 adducts, and it is expressed from the next

From the mixture of vinyl cyclohexene and cyclopentadiene adducts and cyclopentadiene oligopolymer, isolate desirable 5-(3-tetrahydrobenzene-1-yl)-during 2-norbornylene isomer, using simple distillation column or wiped wall still to carry out initial pre-separation is easily.Second step separated by using the polydisc distillation column to realize with more effective.Although the adducts mixture has 80%(weight at least) 5-(3-tetrahydrobenzene-1-yl)-2-norbornylene isomer.As the precursor of the metathesis polymerizable product component of the present composition, careful separation generally can provide has the weight up to 90%(), preferably up to 95%(weight) I a and 1: 1 adducts mixture of I b isomer mixture.The resistates of separation and recovery adducts mixture generally is the isomer of molecular formula II and is lower than 5%, preferably is lower than 1% unreacted 4 vinyl cyclohexene and dicyclopentadiene, also has higher adducts and cyclopentadiene oligopolymer.

Obtain composition of the present invention, can be with 5-(3-tetrahydrobenzene-1-yl)-2-norbornylene isomer mixture generation alkene metathesis polymerizable in the presence of alkene displacement catalyst system and elastomer block copolymer (it is incorporated in the said composition).

Many alkene displacement catalyst systems all are suitable for, and are included in US-A-3933788, US-A-4861848, those catalyst systems of being narrated among US-A-4810762 and the EP-A-374997.

Preferred alkene displacement catalyst system contains a sexavalence tungsten halide, has 0 to 1 oxygen substituting group and alkyl phenoxy substituting group, and it uses with an alkylaluminium cpd or hydrogenation three organotins together, also can use a boron halide promoter arbitrarily in addition.The preferred class of this tungsten halide is the mean value of existing several tungsten halides of being represented by following molecular formula.

In above molecular formula III, each R is respectively up to the alkyl of 10 carbon atoms and preferably up to the branched-chain alkyl of 6 carbon atoms for example sec.-propyl, the second month in a season-butyl or tert-butyl.Particularly preferred R base is a sec.-propyl.Term " X " is a halogen, for example bromine or chlorine, but chlorine preferably.Term " X " is 2 or 4, Y be 0 or 1 and the X+2Y sum be 4.Therefore preferred tungsten compound is tungsten halide (is O as Y) or the oxo tungsten chloride (is 1 as Y) that replaces.Particularly preferred component as the tungsten-containing catalyst system is two 2,6-diisopropyl phenoxy group) tungsten oxychloride and two (2,6-diisopropyl phenoxy group) tungsten chlorides.

When a kind of alkylaluminium cpd used with tungsten halide, it is the chlorination aluminum alkyls preferably, and wherein any alkyl all is the alkyl that comprises 2 to 8 carbon atoms.Particularly preferably be ethylaluminium dichloride and diethylaluminum chloride.Yet what preferably use with tungsten halide is hydrogenation three organotins, particularly hydrogenation trialkyltin, and wherein each alkyl is respectively the straight chain low alkyl group that comprises 3 to 8 carbon atoms.Particularly preferably be hydrogenation three-just-butyl tin.

In suitable alkene displacement catalyst system, alkylaluminium cpd or hydrogenation three organotins to about 2: 1 of the mol ratio of the tungsten halide of above molecular formula III to about 6: 1st, gratifying.

Sometimes it is useful providing a kind of boron halide promoter to alkene displacement catalyst system.Suitable promotor comprises boron trihalides, boron trihalides title complex and four halogenation borates.Preferably boron trifluoride ethyl ether complex, for example boron trifluoride diethyl ether or boron trifluoride dibutyl ether complex compound.The use of boron halide promoter is arbitrarily, and the amount of promotor is that promotor below 10 moles is gratifying to every mole of tungsten halide.When using promotor, the accelerator level of preferred every mole of tungsten halide from about 0.01 mole to about 2 moles boron halide promoter.No matter have or not promotor, the amount of catalyst system to be enough to providing to want the whole monomer mixtures of polymeric is the tungsten halide of about 0.001 mole of % of benchmark to about 5 moles of %, this could be satisfactory.

In the presence of the elastomeric component that the alkene displacement catalyst system and the present composition are arranged by polymerization 5-(3-cyclenes-1-yl)-the 2-norbornylene can suitably produce composition of the present invention.Mix various elastomer materials when preparation and comprise synthetic and natural, polyhutadiene for example, polyisoprene, the random copolymers of ethene and propylene, ethene, the trimer of propylene and a kind of diene monomers, or vinylbenzene, the composition of the polymkeric substance of divinyl and vinyl cyanide, can obtain benefit of the present invention, yet elastomer material only is selected from the elastomer material of some particular types, resemble the segmented copolymer of known vinyl aromatic hydrocarbons and alkadiene, and their selection hydrogenated derivatives.Can be used for the segmented copolymer in the present composition, or as the precursor of selecting the hydrogenant derivative, be some thermoplastic elastomer, it is characterized in that at least one is a main at least polymerization of vinyl compound aromatic hydrocarbon block (being commonly referred to as the A block) and another is at least main polymerization conjugated alkadiene block (being commonly referred to as the B block) at least.

Monomeric vinyl aromatic hydrocarbons as the A block has a vinyl, i.e. C=CH ₂Base, it directly is connected with aromatic ring, and it comprises 12 carbon atoms at the most.Preferred vinyl aromatic hydrocarbons is for example those homologues of molecular formula IV of vinylbenzene and vinylbenzene homologue.

Each R wherein ¹Be respectively hydrogen or comprise alkyl up to 4 carbon atoms.The example of described vinyl aromatic hydrocarbons is a vinylbenzene, and p-methylstyrene is right-ethyl styrene ,-propylstyrene, alpha-methyl styrene, α-ethyl styrene and 2,4-dimethyl styrene.Vinylbenzene and alpha-methyl styrene are preferred class vinyl aromatic hydrocarbons, but particularly preferably are vinylbenzene.

Each A block of segmented copolymer is respectively based on the polymeric vinyl aromatic hydrocarbons at least, and preferably homopolymerization.Yet on the other hand, one or more A blocks are such blocks, and the main vi-ny l aromatic monomers of the monomer of some of them B block and block A carries out copolymerization.Such block is called as " transition section " and has at least 85% mole, preferred at least 93% mole vinyl aromatic hydrocarbons and any remainder is the conjugated alkadiene of B block.The A block that contains the aromatic vinyl hydrocarbon mixture also is useful but is not preferred.With regard to broadly to this segmented copolymer, the molecular-weight average of A block is generally from about 1000 to about 125,000, but the molecular weight of the more frequent A block that runs into is from about 5000 to about 60,000.

Each B block of segmented copolymer is respectively at least based on the block of polymeric chain diene.As the principal monomer alkadiene of B block is conjugated alkadiene those alkadienes of following molecular formula for example of 8 carbon atoms at the most

Wherein the definition of R ' is the same.The illustration of this alkadiene is 1,3-butadiene (divinyl), 2-methyl isophthalic acid, 3-divinyl (isoprene) 2,3-dimethylbutadiene, 1,3-pentadiene (piperylene), 1,3-octadiene and 2-methyl isophthalic acid, 3-hexadiene.Preferred conjugated alkadiene is under the B block situation of divinyl and isoprene transition, and each B block is main at least polymeric alkadiene.At least 85% mole preferred at least 93% mole the diene of polymeric chain, remaining is the embedding face A of aromatic vinyl.Although the block of the block of transition and blended alkadiene also is gratifying, the B block of homopolymer preferably.Within polymeric alkadiene block, have the polymerization of two kinds of forms and generally can observe.In being called 1.4 polymerizations, each carbon atom of 4 carbon nuclears of alkadiene all is incorporated in the polymer chain, and this chain comprises two carbon atoms that connected by ethylenic linkage then.In 1.2 polymerizations, this polymerization only comprises a carbon-to-carbon double bond of conjugated alkadiene.The carbon atom of this pair key is incorporated in the polymer chain then, so this chain contains a side thiazolinyl.These two kinds of pattern polymeric controls are scopes well known in the art.Preferred segmented copolymer is those multipolymers of the result of each B block polymerization.Particularly preferred those segmented copolymers are that about 8% to about 50% unit is to be produced by 1,2 polymerization in each B block.The molecular-weight average of a B block is suitable for from about 10000 to about 450,000, and preferably from about 10000 to about 150,000.

Within segmented copolymer, A block content is not more than 55%(weight) (is benchmark with whole segmented copolymer).Preferably, the A block from about 10% to about 40%(weight) (with same benchmark).The whole molecular-weight average of segmented copolymer is equivalent to about 11,000 to about 450,000, but preferably approximately 35,000 is to about 300,000.These molecular-weight average can be measured by routine techniques, example gel permeation chromatography or with low-angle light scattering method or their combination.

The structure of segmented copolymer will depend on the polymerization process that is used for producing this polymkeric substance.Segmented copolymer is called as line style in a modification, and what will be illustrated is to be produced by the sequential polymerization of block.As an example, in the production of triblock copolymer, the vinyl aromatic hydrocarbons of A block is by means of a kind of initiator, and preferred a kind of hydrocarbyl lithium compound carries out polymerization.Introduce the conjugated alkadiene of B block then, introduce the vinyl aromatic hydrocarbons of other second A block subsequently.Such triblock copolymer is represented as ABA.Two blocks or diblock copolymer can be introduced subsequently as the conjugated alkadiene of B block and produce by carry out the A block polymerization by means of alkyl lithium initiator.Such polymkeric substance is represented as AB.Before adding another kind of monomer, finish a kind of monomeric polymerization basically and produce homopolymer block.Yet,, will produce the transition block if before the polymerization of any block is finished, just introduce the monomer of next block.Adopt similar sequential polymerization technology to produce and be expressed as ABABA, ABAB, the segmented copolymer of ABABABA or even the polymkeric substance of higher block.The production of the production of segmented copolymer, especially those suitable high molecular weight block copolymer also can be finished by using a kind of coupler coupling or connecting the polymer chain that increases.Use the difunctionality coupler, for example dihalo alkane will cause producing simple linear polymer, but have three or the coupler of multiple functional radical more if use, for example, many vinyl aromatic hydrocarbons, the alkyl ester of silicon tetrahalogen or dicarboxylic acid will cause forming various being called as " star ", the segmented copolymer of " radiation shape " or " chain ".

These segmented copolymers be that prior art is known and the characteristic of this base polymer and preparation method at US3251905, US3390207, US3598887, US4219627, US4408357, US4497748 and US4426495 illustrated.

The most common segmented copolymer type that runs into is polystyrene-poly divinyl (SB), polystyrene-poly isoprene (SI), the line style sequential polymerization thing of polystyrene-poly divinyl-polystyrene (SBS) and polystyrene-poly isoprene-polystyrene (SIS) type.The title of this same type is usually used in the segmented copolymer of other type, for example SBBS or (SB) ₂(simple linear polymer that is used for coupling) and (SB) _n(being used for the radiation shape polymkeric substance of the SB segment of n arm) around a central core.These segmented copolymers are general and produce in enormous quantities, they by Shell Chemical Company with KRATON

Thermoplastic elastomer is sold.

Yet extensively improved the alkene replacement product of shock-resistance, the character of segmented copolymer is very important.Can provide that the A block is quite little than whole copolymer molecule in those multipolymers of best shock-resistance.The segmented copolymer that preferably is used for the present composition is such polymkeric substance, and wherein the molecular weight of A block is approximately less than 20,000, and more preferably approximately less than 12,000, and the B block is a polyisoprene.Preferably polyisoprene blocks is by at least 90%, and more preferably at least 95% 1.4 polymerizations produce.

The selection hydrogenant derivative of the above segmented copolymer also is useful in composition of the present invention.In order to prepare these derivatives, select hydrogenated block copolymer with a kind of method of aliphatic unsaturated link(age) of each the B block that is enough to hydrogenation about 80% to about 99%, carry out hydrogenation and be not more than 25% but the aromatics of each A block is unsaturated, preferably be not more than 5%.This hydrogenation can be finished by US3113986 and the disclosed ordinary method that exemplifies of US4226952.Select the hydrogenant segmented copolymer to be determined by the structure of segmented copolymer precursor and " apparent " structure of aliphatic block usually.Therefore the selection hydrogenation of SBS polymkeric substance will produce a kind of polymkeric substance with hydrogenant mid-block, its " picture on the surface " polyethylene (under the mid-block situation by 1.4 polymerizations production) and ethylene/butylene copolymers are (random 1,2 and 1,4 polymerization ratio and under the mid-block polymkeric substance situation of producing).These select the hydrogenant segmented copolymer to refer to SES and SEBS respectively.The corresponding hydrogenant diblock copolymer of selecting will be called SE or SEB.Select hydrogenant mid-block camber 1,4 polymeric SIS segmented copolymer to be called as the SEPS polymkeric substance, this is because of the similarity to a kind of ethylene/propene copolymer hydrogenant mid-block.The most common selection hydrogenated block copolymer that runs into is linear SES and SEBS type, wherein the mid-block unit is about 20% to about 90%, and preferably approximately 30% is to about 50% mid-block type (being produced by 1,2 polymerization), its all the other are to be produced by 1,4 polymerization basically.The illustration of a kind of selection hydrogenant " radiation " type copolymer be corresponding exemplifying (SE) n or (SEB) n wherein n represent to select existing SB arm number before the hydrogenation.Select hydrogenant segmented copolymer and characteristic thereof in the prior art field, to know along with production in enormous quantities.For example, some selection hydrogenant segmented copolymer is with KRATON G by Shell Chemical Company

Thermoplastic elastomer is sold.

When selecting the hydrogenant segmented copolymer to be used for composition of the present invention, preferably use and compare multipolymer with whole molecule with quite little A block.Having A block molecule amount, to be lower than about 30,000 selection hydrogenant segmented copolymer be preferred, and to be lower than about 20,000 selection hydrogenant segmented copolymer be particularly preferred and have A block molecule amount.The preferred contained divinyl of hydrogenant segmented copolymer of selecting passes through 1,2 and 1.4 polymerizations and deutero-" B " block, and the per-cent that promptly has the block of EB configuration is about at least 45%(weight) and less than about 85%(weight).

Select the hydrogenant derivative to be added to when true quantitative segmented copolymer or its and contain 5-(3-tetrahydrobenzene-1-yl)-polyblend of 2-norbornylene in the time, just can produce composition of the present invention, said composition also can contain alkene metathesis polymerizable linking agent and, contain dicyclopentadiene arbitrarily.Open loop or metathesis polymerizable are produced the polymerisate that is mixed with elastomer material under the conventional polymeric condition of this mixture.The ratio of elastomer material in whole composition be suitable for whole composition weights be benchmark about 2% to about 10%(weight).Preferred elastomer material ratio is about 4% to about 8%(weight).

Composition of the present invention be tough and tensile thermosetting polymer can be used for conventional use this base polymer with occasion but it especially can be used for polymeric articles and may be subjected to the ballistic application scenario of other object.The special applications of composition of the present invention comprises part and the shell that automobile is used.

The present invention is further described by following proof embodiment (they should not be considered to limit the present invention) and Comparative Examples (not being the present invention).

Embodiment 1

Equimolar dicyclopentadiene and 4 vinyl cyclohexene mixture are heated 4 to 4.5 hours in 240 ℃ in an autoclave.Reaction product is diluted then by an alumina filled bed so that remove the tert-butyl catechol stopper of being introduced by reactant with tetrahydrobenzene.The gained mixture in a wiped wall still at 400pa(3mmHg) distill under pressure and 90 ℃ and extract the lighting end that contains unreacted vinyl cyclohexene and dicyclopentadiene out.This distillate sample of 50 grams is carried out vacuum distilling with 10-tower tray Oldershaw tower provide four kinds of cuts.Represent through gas chromatographic analysis, the 4th kind of cut of 65 grams is by 0.15% dicyclopentadiene, in 88.3%-5-(3-tetrahydrobenzene-1-yl)-the 2-norbornylene, 6.1% outer-5-(3-tetrahydrobenzene-1-yl)-the 2-norbornylene, two kinds of additional components, amount is 1.9% and 2.4%, it is believed that it is the isomer adducts of following molecular formula

Several additional component summations are roughly 0.4%, and about 0.4% three cyclopentadiene and about 0.4% mole of unidentified component are formed.The nuclear magnetic resonance spectroscopy of this cut shows the above interior adducts of about 87 moles of %, the isomer adducts of about 9% above outer adducts and about 5% above molecular formula II.

The embodiment II

Produce the moulded product of many present compositions and estimate.Moulded product is by a kind of production in two universal methods.The solution of elastomerics in monomer under condition of nitrogen gas with the dry monomer of suitable proportion and dry elastomer-bonded together and this elastomerics of mixed dissolution prepare.In monomer, also dissolve a kind of oxidation inhibitor for example 2 in some cases, 6-two-tertiary butyl-4-methylphenol, it is measured from 0.2% to 0.5%(weight).

Universal method-10cm * 10cm(4 " * 4 ") sheet metal forming

In the vacuum pressure loft drier under nitrogen, two (2 of the measured quantity in advance of in the clear liquid bottle of 30ml dring silicon alkanisation, packing into, 6-di-isopropyl phenoxy group) two tungsten oxychlorides (7% weight, in monomer), boron trifluoride dibutyl ether compound (1% weight is in monomer) thereby and the dry elastomer solution in other monomer 25 gram monomer solutions altogether are provided.The gained mixture is carried out powerful mixing.In second clear liquid bottle, add the elastomerics in tri-butyl tin hydride (tin is 4: 1 mol ratios to tungsten) and the 25 gram monomers.

Allow these two kinds of static placements of solution at least 5 minutes so that bubble rises to the top of bottle.Then this solution is poured into the double shell plastic barrel of 50ml band edge lid, inserted back piston then.This plastic barrel is put into the jar of a thread ending cover then with the-tractable static mixer of 15cm(6 ").Seal this jar then and under nitrogen, it be transferred to lattice Lars, west, the general Rec of Manostat Plexglass(from loft drier) glove box.

This plastic barrel is shifted out from jar and installs on the Comprotec liquid spray gun, and the end cap of plastic barrel replaces with static mixer, then polyblend is passed mixing tube and is expelled to a preheating in the glove box, with in the mould of nitrogen purging.Observation in the mould temperature and write down time of temperature rise.Temperature rise was later stayed sample 5 minutes and is disconnected well heater then and opens mould in mould.With that the plate of moulding is taken out from mould in some cases but then allow in other cases plate stayed in the mould and reach till 80 ℃ until temperature.Typical mold temperature is 100 ℃ to 140 ℃ (before the temperature rise), monomer generally is 2000: 1 to 6000: 1 to the mol ratio of catalyzer, representational is 4000: 1, and boron trifluoride (if with) is 0.05-0.15 to the mol ratio of catalyzer, and representational is 0.075: 1.

This mould is by being clipped in 15cm * 15cm(6 in the mould " * 6 ") silicon rubber flexible heater in the stainless steel plate and outside insulcrete form.Thermopair is inserted between plate and the flexible heater.A soft-teflon beading packing ring, the thickness that 0.292cm(0.115 ") diameter is used to switchboard is about 0.279cm(0.110 ").Plate and packing ring are fixed together with big clip, and this mould uses the injection member (being used for injection and flash) of coaxial double-screw type, has injection member in the bottom.

Universal method-big sheet metal forming

General-250ml bottle spends the night at the baking oven inner drying then with toluene and acetone rinsing in the vacuum pressure loft drier, in this bottle, pack into the tungsten catalyst solution (every mole of tungsten about 2000 is to about 5000 mole of monomer) of above-described predetermined amount, boron trifluoride in the solution (if you are using) (every mole the about 0.05-of tungsten about 0.15 mole) and cross-linking monomer (if you are using).Add other monomer or the rubber solutions in monomer 70 gram monomer mixtures are provided.In second bottle, add 70 gram monomer or rubber solutions and tri-butyl tin hydrides (representational tin is 4: 1 to the mol ratio of tungsten).The inclusion of each bottle is all thoroughly mixed, and the cup that bottle is placed on loft drier makes the solution degassing through vacuum cycle several times then.

Every kind of solution is all poured in the plastic barrel of 75ml band edge lid and inserted a back piston then.Remove end cap and after removing excessive nitrogen, lid is resetted, then this plastic barrel is connected with a pair of barrelling system.Then the tube that has sealed is shifted out from loft drier.

Body plan one mould in a fume cupboard, it is by being clipped in 18 * 28cm(7 " * 11 ") watlow silicon rubber flexible heater in the aluminium sheet has the body plan of external insulation plate and forms.End template has thermopair on its surface, and front template has a thermopair to insert on its limit near the plate at center by the hole.Internal surface is handled with a kind of releasing agent, and the packing ring of being made by 0.3cm(1/8 ") teflon beading is placed between the plate approximately from outer rim 1.9cm(0.75 ") part.This plate has injection and flash hole, and mould is fixed together with big clip.Being heated to required mold temperature then with nitrogen cleaning mould before the moulding, generally is 100 ℃ to 120 ℃.

The end cap of removing plastic barrel also replaces with a static mixing organ pipe.This tube is docked on one " rifle ", extrudes two monomer solutions from this tube, this solution passes the mould that static mixer enters preheating, writes down inject time, temperature rise temperature and temperature rise time.When disconnecting well heater sample stayed in the mould and to take out plate in 5 minutes then.Approximately be cooled to about 80 ℃ in 10-15 minute can allowing plate stayed in the mould until mould in some cases.

Comparative Examples I-embodiment III-IV

Universal method

Produce multiple composition of the present invention as stated above and estimate shock-resistance.Adopt test method to measure the shock-resistance of two kinds of general types.Method with a kind of similar ASTM-D3029 is measured Gardner's impact value, produces about 0.3cm(1/8 inch of a selected composition with conventional forming method) thick plate, the cylindrical bar of a known weight is fallen on the plane of plate from predetermined height.This test can be measured the shock-sensitive degree of said composition and be noted crack conditions during by impact grinding at sample.Second type shock test, notched izod test is to be measured by the test that is similar to ASTMD-256, about 0.3cm(1/8 inch is used in this test) thick moulding sample and jagged at an one edge.Impact the breach limit of sample from predetermined height with a pendulum.This experimental measurement is at the indentation, there required energy of this sample that ruptures.

Although these two tests all are conventional, yet they have measured the different impact break values of sample.Common a kind of composition can provide gratifying result that another kind test then can not to a kind of test.Rarely found a kind of composition can both provide gratifying result in two kinds of tests.

The Comparative Examples I

Having in the presence of various vinylbenzene and the butadiene block copolymer by polymerization 5-(3-tetrahydrobenzene-1-yl)-2-norbornylene mixture prepares composition.Segmented copolymer or elastomeric type are as follows:

Elastomerics A: link coupled, linear three blocks (SB) ₂The type multipolymer

Elasticity B:(SB) ₂Type radiation segmented copolymer has 3 polyhutadiene/polystyrene arm,

Elastomerics C: be similar to elastomerics B, per molecule has 3 or 4 arms.

Measure the Gardner and the notched izod shock-resistance of these compositions, the results are shown in the table I, wherein the molecular weight of styrene block and other embodiment's all is weight-average molecular weight.

The table I

Elastic body styrene block Gardner impacts izod impact J/cm

(weight %) (Mw * 10 ^-3) J (one pound of inch) (one pound/inch of foot)

There are not (0)-39.6 (350) 0.27 (0.5)

A(5) 10.2 45.2(400) 0.75(1.4)

(6) 10.2 33.9(300) 0.21(0.4)

(7) 10.2 33.9(300) 0.91(1.7)

(8) 10.2 3.4(30) 0.16(0.3)

(4) 16.1 - 0.27(0.5)

(6) 16.1 10.2(90) -

B(6) 11.5 33.9(300) 0.27(0.5)

(8) 11.5 5.6(50) 0.27(0.5)

C(6) 12.0 13.6(120) -

(6) 21.0 <6.8(<60) 0.37Y(0.7)

Many results by Gardner's shock test gained are considered to gratifying.Then unsatisfactory from the result of izod impact test gained.

The embodiment III

Produce and a series ofly contain the composition of vinylbenzene and isoprene block copolymer and measure according to the method for Comparative Examples I.Used elastomerics, elastomerics O is linear, link coupled three blocks (S-I) ₂The type multipolymer.In the table II, provide measurement result.

The table II

Elastic body styrene block Gardner impacts izod impact J/cm

(weight %) (Mw * 10 ^-3) J (in-lb) (ft-lb/inch)

D(16) 10.6 33.9(300) -

(7) 10.6 27.1(240) 5.77(10.8)

(6) 10.8 30.5(270) -

(7) 10.8 - 4.4(8.2)

(6) 10.9 31.6(280) -

(7) 10.9 - 4.7(8.8)

(6) 15.5 3.16(280) -

All be considered to gratifying from the result of Gardner's shock test and izod impact test gained.

The embodiment IV

Produce and a series ofly contain the segmented copolymer of selecting hydrogenant vinylbenzene and divinyl and measure according to the method for embodiment III.Used elastomeric component type is as follows.

Elastomerics E: linearity, link coupled (SEB) ₂The type multipolymer

Elastomerics F: linearity, order SEBS type multipolymer

Measurement result is shown in the table III.

The table III

Elastic body styrene block Gardner impacts izod impact J/cm

(weight %) (Mw * 10 ^-3) J (one pound of inch) (one pound/inch of foot)

E(4) 7.2 45.2(400) 0.5(0.9)

(5) 7.2 40.7(360 ^*) 0.7(1.3 ^*)

(6) 7.2 39.6(350) 0.8(1.5)

(7) 7.2 35.0(310 ^*) 6.8(12.7) ^*

(8) 7.2 36.2(320) 5.9(11.1)

F(4) 7.2 45.2(400) 0.4(0.7)

(5) 7.2 38.4(340) 7.85(14.7)

(6) 7.2 33.9(300) 1.2(2.2)

(7) 7.2 24.9(220) 0.32(0.6)

(8) 7.2 14.7(130) 0.37((0.7)

(5) 9.4 32.8(290) 1.6(3.0)

(6) 9.4 13.6(120) 0.43(0.8)

(7) 9.4 10.2(90) 0.37(0.7)

(8) 9.4 20.3(180) 0.43(0.8)

(4) 10.1 - 10.6(13.3)

(5) 10.1 39.6(350) 1.2(2.2)

(6) 10.1 28.2(280) 0.32(0.6)

(7) 10.1 21.5(190) 0.37(0.7)

(8) 10.1 16.9(150) 0.5(0.9)

(4) 29.0 31.6(280) 0.27(0.5)

(6) 29.0 33.9(300) 2.1(4.0)

* the mean value that an above moulded product is tested, the izod impact value is gratifying in all cases, Gardner's impact value also is gratifying.

The Comparative Examples II

Prepare the mixture of adducts and cyclopentadiene oligopolymer according to the method for embodiment I by heating 4 vinyl cyclohexene and dicyclopentadiene, prepare a metathesis polymerizable product by this mixture.Do not separate, use with the similar method of embodiment II and this mixture is carried out polymerization having in the presence of the 7% weight of elastomer E.Impacting income value by the Gardner is the 15.8(140 in-lb), impacting income value by notched izod is 0.43J/cm(0.8 ft-lb/inch).

Claims

1, a kind of thermoset polymer compositions, it contains the metathesis polymerizable product of a kind of 5-(3-cyclohexene-1-yl)-2-norbornylene and accounts for a kind of impact modifying agent of whole composition 2 to 10% weight, and it is selected from elastic block copolymer and a kind of derivative of selecting the elastomeric block copolymers of hydrogenant aromatic vinyl hydrocarbon compound and conjugated alkadiene of a kind of aromatic vinyl hydrocarbon compound and isoprene.

2, a kind of composition according to claim 1, wherein impact modifying agent is the segmented copolymer of a kind of vinylbenzene and isoprene.

3, a kind of composition according to claim 2, wherein the molecular weight of each polystyrene block is less than 20,000.

4, a kind of composition according to claim 2 or 3, wherein segmented copolymer is a linear block copolymers.

5, a kind of composition according to claim 2, wherein segmented copolymer is a triblock copolymer at least.

6, a kind of composition of 5 as requested, wherein segmented copolymer is the ABA of a kind of vinylbenzene and isoprene or (AB) ₂Segmented copolymer.

7, a kind of according to claim 2,3,5 or 6 composition, wherein at least 90% unit is to be produced by 1,40 polymerization in each polyisoprene blocks.

8, a kind of composition according to claim 1, wherein impact modifying agent is the selection hydrogenant derivative of the elastomeric block copolymers of a kind of aromatic vinyl hydrocarbon compound and conjugated alkadiene, and the aliphatic unsaturated link(age) that it results from least 80% elastomeric block copolymers carries out hydrogenation but be not more than 25% elastomeric block copolymers aromatics unsaturated link(age) carrying out hydrogenation.

9, a kind of composition according to Claim 8, wherein properties-correcting agent is the selection hydrogenated derivatives of a kind of vinylbenzene and divinyl or isoprene.

10, a kind of composition according to claim 9, wherein the molecular weight of each styrene block is less than 30,000.

11, a kind of composition according to Claim 8, wherein properties-correcting agent is a kind of selection hydrogenated derivatives of linear block copolymers.

12, a kind of composition according to claim 11, wherein selecting the hydrogenant segmented copolymer is a kind of triblock copolymer at least.

13, a kind of according to Claim 8,9,10,11 or 12 composition, wherein hydrogenant alkadiene amount be the multipolymer gross weight at least 45% to less than 85%.

14, a kind of according to Claim 8,9,10,11 or 12 composition, wherein selecting the hydrogenant segmented copolymer is a SEBS or (SEB) ₂The polymkeric substance of type.

15, a kind of according to claim 1,2,3,5,6,8,9,10,11 or 12 composition, wherein the amount of impact modifying agent is that total composition is 4% to a 8%(weight of benchmark).

16, a kind of method of producing the thermosetting polymer product is included in a kind of alkene metathesis polymerization catalyst system and 2 to 10%(weight) there is 5-(3-tetrahydrobenzene-1-yl down in said impact modifying agent)-the alkene metathesis polymerizable of 2-norbornylene.