CN1084340C - Preparation of polydicyclopentadiene - Google Patents
Preparation of polydicyclopentadiene Download PDFInfo
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- CN1084340C CN1084340C CN97106423A CN97106423A CN1084340C CN 1084340 C CN1084340 C CN 1084340C CN 97106423 A CN97106423 A CN 97106423A CN 97106423 A CN97106423 A CN 97106423A CN 1084340 C CN1084340 C CN 1084340C
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- C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
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Abstract
The present invention provides a method for preparing dicyclopentadiene. Raw materials are proportionally prepared into a component A and a component B, wherein the component A contains bimetal composite catalysts and additive agents, and the component B contains compounding aluminum alkyl zinc halide as activating agents, polymerization time regulating agents and additive agents. At least one component in the component A and the component B contains dicyclopentadiene as a raw material. Polydicyclopentadiene is prepared from two prepared components by a reaction injection molding forming process. The catalyst system of the present invention has low purity requirement for the dicyclopentadiene and has the advantages of high polymerization conversion rate and wide polymerization operating range. Products have the advantages of no odor, good heat resistance, good surface smoothness, high impact resistance, high bending modulus and no need for post treatment.
Description
The present invention relates to a kind of preparation method of polydicyclopentadiene, is particularly suitable for raw material is mixed with A, B two components by the prescription requirement earlier, adopts the polymerization process of reaction injection molding to make the polydicyclopentadiene product.
In prior art, polydicyclopentadiene (PDCPD) is succeeded in developing by U.S. Hercules company at first, the mid-80 U.S. B.F.Goodrich company also develops the polydicyclopentadiene product, and this two company develops jointly out the product of the multiple trade mark, tens series respectively with Japanese Supreme Being people company and Nippon Zeon Co., Ltd. subsequently.
Polydicyclopentadiene is formed by dicyclopentadiene (DCPD) ring-opening polymerization, exothermic heat of reaction and speed of response are very fast, under the condition that does not heat, after catalyzer adds, polyreaction can be finished in moment, and because the viscosity low (about 0.3Pas) of raw material dicyclopentadiene, so the polymerization of dicyclopentadiene is particularly suitable for adopting reaction injection molding (RIM) process.
The catalyst system of dicyclopentadiene polyreaction has many kinds, the compound and the chlorination aluminum alkyls of verified tungsten the most effectively or molybdenum.United States Patent (USP) 4400340 and 4520181 has been introduced raw material dicyclopentadiene and other component by bifilar stream reaction injection molding technology, wherein a plume comprises catalyzer, and another plume contains activator and dicyclopentadiene, mixes at the RIM head, inject mould, at short notice polymerization rapidly.Catalyzer is tungsten or molybdenum halogenide, and activator is an alkylaluminium cpd.United States Patent (USP) 4981931 and 5082909 has been introduced employing WOCl
4-x(OAr)
x(x=1～3) are catalyzer, and activator is a tin alkyl, make polydicyclopentadiene by the RIM process.It is WCl that United States Patent (USP) 5071812 has been introduced catalyzer
6Or WOCl
4, activator is Y
+[BH
mZ
n]
-The hydrogen boron compound, Y
+Be the organo-metallic ion, Z is alkyl or cyano group halogenide, m＞0, and m+n=4 makes polydicyclopentadiene by the RIM process.But catalyst system the having relatively high expectations that aforesaid method is used to dicyclopentadiene, generally need high-purity dicyclopentadiene raw material, and polymerisation conversion is lower, the goods frowziness, poor surface smoothness, poor heat resistance, polymerization velocity is fast, operational difficulty, the polydicyclopentadiene product that makes generally need post-treatment to handle.
The purpose of this invention is to provide a kind of employing double-metal composite catalyst and composite activating agent, prepare the method for polydicyclopentadiene by the RIM process.This catalyst system is lower to the purity requirement of raw material dicyclopentadiene, the polymerisation conversion height, and the polydicyclopentadiene goods do not have stink, good heat resistance, the converging operation wide ranges, polymer surfaces smooth finish is good, generally need not to carry out aftertreatment.
In order to realize this purpose, the present invention adopts before polyreaction, earlier raw material is mixed with A, B two components by a certain percentage, wherein the A component contains two kinds of transistion metal compounds and additive, the B component contains the compound aluminum alkyls zinc of activator halogenide, polymerization time conditioning agent and additive, and has at least in the component among the A, B component and contain dicyclopentadiene.The A for preparing, B two components are respectively after the volume pump metering, mix with the certain proportion bump at the RIM head, inject mould down in low temperature (30 ℃), low pressure (3.0MPa), rapid reaction polymerization and moulding thereupon obtain the polydicyclopentadiene goods after the demoulding in mould.
Preparation of catalysts method of the present invention: halogenide, transition metal halide, solvent toluene and the solubility promoter of tungsten or molybdenum or tantalum are joined in the also usefulness there-necked flask of nitrogen protection that has reflux condensate device, agitator, heating system by a certain percentage together; under 60～150 ℃ of temperature, make its reaction; the hydrogen chloride gas water that produces in the reaction absorbs; reacted 16～20 hours, make as shown in the formula double-metal composite catalyst.
M
1(OAr
1)
n1·M
2(OAr
2)
n2·X
n3
In the formula: M
1Be a kind of in tungsten, molybdenum, the tantalum;
M
2Be a kind of in titanium, vanadium, the zirconium;
X is a halogen;
Ar
1And Ar
2Be a kind of in alkyl, cycloalkyl, aromatic base, the aralkyl;
N1 is 0～6, and n2 is 0～4, and n3 is 1～6.
The halogenide of tungsten or molybdenum or tantalum: transition metal halide: solvent toluene: solubility promoter=1: (0.5～2): (4～8): (0.2～2) (weight ratio).M
1: M
2=(0.2～2.5): 1 (weight ratio) is preferably (0.5～2): 1 (weight ratio).Solubility promoter of the present invention is a kind of in butanols, tertiary amyl alcohol, phenol, the p-tert-butylphenol.Used raw material all needs dehydration in advance.The catalyzer that makes need be used nitrogen protection.
M in the double-metal composite catalyst of the present invention
1Be tungsten, M
2It is titanium.Can be with WCl
6, TiCl
4, the reaction of solvent toluene, solubility promoter p-tert-butylphenol, form W (OAr
1)
N1Cl
1And Ti (OAr
2)
N2Cl
2Two kinds of transition metal compound aromatic bases, this compound make metal carbene be easy to form, and impel the crosslinking polymerization of cycloolefin.Tungsten: titanium=(0.5～2): 1 (weight ratio), best is (0.8～1.1): 1 (weight ratio).WCl
6: p-tert-butylphenol=1: (0.5～2) (weight ratio), best is 1: (0.9～1.2) (weight ratio).
The compound method of A component among the present invention: the same dicyclopentadiene of above-mentioned double-metal composite catalyst, stablizer and additive are added in the there-necked flask by a certain percentage, mix, total system needs dry and uses nitrogen protection.Double-metal composite catalyst: dicyclopentadiene: stablizer: additive=1: (0～1500): (0.001～0.01): (10～100) (weight ratio).
The raw material dicyclopentadiene is mainly derived from from coal tar benzene overhead distillate and reclaims or petroleum cracking system ethylene by-product product C
5Separate in the cut.The present domestic hundreds of thousands of ton C that has approximately
5Secondary liquid, major part is burnt as fuel, has caused the huge waste of resource.C
5Contain dicyclopentadiene 15～17% approximately in the secondary liquid, its separation available general method of purifying carries out, as distillation method, absorption method, reduction method etc.The purity of dicyclopentadiene height has determined that not only dicyclopentadiene whether can polymerization, but also can influence the performance quality of polydicyclopentadiene.Major cause is C
5Contain poly-impurity of resistances such as superoxide, alcohol, ether and water in the secondary liquid, and other olefin oligomer etc., therefore the patent before all requires the purity of raw material dicyclopentadiene greater than 99%.
C of the present invention
5Distillation method is adopted in the purification of secondary liquid, separates and removes low-boiling-point substance.Remove the C of low-boiling-point substance
5Raffinate contains the dicyclopentadiene about 40% approximately, uses two-tower rectification again, removes lower boiling and high-boiling-point impurity, finally obtains purity greater than 97%, and water-content is less than the dicyclopentadiene raw material of 100ppm.Because unsaturated dicyclopentadiene is easily oxidized, form resistance polyperoxide etc., so need to add oxidation inhibitor such as 264-oxidation inhibitor in the dicyclopentadiene, general consumption is 0.5～5% of a dicyclopentadiene weight, reasonable is 0.5～1.0%.The dicyclopentadiene storage tank need be used nitrogen protection.
Stablizer plays chelatropic reaction with transition metal, can stop the formation of metal carbene, prevents the dicyclopentadiene polymerization.Stablizer is a kind of in benzyl formonitrile HCN, benzyl acetonitrile, methyl ethyl diketone, the tetrahydrofuran (THF).Catalyzer WCl
6: stablizer=1: (0.001～0.01) (weight ratio) is preferably 1: (0.005～0.009) (weight ratio).It is stable that the A component that is mixed with can keep in some months, can not produce gel polymerisation.Additive can be fire retardant, softening agent, tackifier, filler, pigment etc.Fire retardant is phosphorus systemization thing and halogen compounds, as decabromodiphynly oxide, tributyl phosphate etc.; Softening agent is dibutylester, dimethyl ester etc.; Tackifier are ethylene-vinyl acetate copolymers etc.; Filler is glass fibre, carbon fiber etc.; Pigment is reactive pigment or azo class pigment.
The compound method of B component among the present invention: dicyclopentadiene, activator, polymerization time conditioning agent and additive are added by a certain percentage dry in advance also with in the there-necked flask of nitrogen protection; mix; control mixes temperature between 30～40 ℃, and is standby after mixing.Control 30～40 ℃ the effect that temperature can prevent to destroy the polymerization time conditioning agent that mixes.Dicyclopentadiene: activator: polymerization time conditioning agent: additive=(0～500): 1: (10～100): (1～100) (weight ratio).Activator is compound aluminum alkyls zinc halogenide, can be a kind of mixture that matches in a kind of and zinc ethyl, chloroethyl zinc, iodine zinc ethyl in triethyl aluminum, aluminium diethyl monochloride, ethyl aluminum dichloride, the iodine aluminium triethyl.The polymerization time conditioning agent can be a kind of of diethylene glycol dimethyl ether, dibutyl ethylene glycol ether or both mixtures.Additive can be fire retardant, softening agent, tackifier, filler, pigment etc.Fire retardant is phosphorus series compound and halogen compounds, as decabromodiphynly oxide, tributyl phosphate etc.; Softening agent is dibutylester, dimethyl ester etc.; Tackifier are ethylene-vinyl acetate copolymers etc.; Filler is glass fibre, carbon fiber etc.; Pigment is reactive pigment or azo class pigment.
Activator can impel the formation of the transition metal carbene of catalyzer, thereby improves its activity.The general alkyl halide that adopts is as triethyl aluminum, aluminium diethyl monochloride, phenodiazine aluminium triethyl etc.But various alkyl halides are to dicyclopentadiene polymeric gel time length difference.The present invention selects aluminium diethyl monochloride and zinc ethyl composite activating agent for use, because the aluminium diethyl monochloride activation is stronger, polymerization velocity is very fast, and the zinc ethyl activation relatively a little less than, slow down polymerization velocity, yet in case reaction take place, can show stronger polymerization activity, so composite activating agent not only can be controlled gel time, and improves the polymerization velocity and the degree of crosslinking of dicyclopentadiene, make goods not have stink.Aluminium diethyl monochloride: zinc ethyl=(10～25): 1 (weight ratio) is preferably (15～20): 1 (weight ratio).
For controlled polymerization reaction times effectively, make feed liquid gel polymerisation not before being full of mould, need to add the polymerization time conditioning agent.The polymerization time conditioning agent generally is compounds such as alcohol, ketone, ether, ester, amine, nitrile.The present invention adopts diethylene glycol dimethyl ether, dibutyl ethylene glycol ether or both mixtures, the span of control broad of this compound or both mixtures.Diethylene glycol dimethyl ether: dibutyl ethylene glycol ether=(0.1～10): 1 (weight ratio).The consumption of polymerization time conditioning agent also has considerable influence to the speed of polyreaction, and consumption is too much, can make the dicyclopentadiene can't polymerization, becomes stopper; Consumption is very few, feed liquid may take place do not fill with mould gel polymerisation promptly takes place.General controlled polymerization time conditioning agent: aluminium diethyl monochloride=(10～100): 1 (weight ratio) is preferably (15～25): (weight ratio).
Reaction injection molding (RIM) technology is that a kind of monomer or low viscosity copolymer liquid state directly injects mould, carry out polyreaction fast, it unites two into one the molding process of polyreaction and polymkeric substance, have that moulding is fast, the cycle is short, power consumption less, characteristics such as low, the good product quality of cost.
Dicyclopentadiene is to carry out polymeric by displacement catalysis ring-opening polymerization mechanism, the exothermic heat of reaction amount is big and polymerization velocity is fast, can finish polymerization in several seconds, and because dicyclopentadiene and catalyst system are made into feed liquid, be liquid under the room temperature, viscosity low (about 0.3Pas), these character make the polymerization of dicyclopentadiene be particularly suitable for the RIM process.
The preparation of polydicyclopentadiene of the present invention is that the A that will prepare in advance, B two components are after the volume pump metering, have at least a component to contain the raw material dicyclopentadiene in A, B two components, mix through RIM head bump, the material temperature is 20～40 ℃, is preferably 25～30 ℃; Pressure is about 3.0MPa, injects mould, and the in-site polymerization temperature is 20～100 ℃, is preferably 60～80 ℃, finishes polymerization and curing molding with this understanding fast, obtains the polydicyclopentadiene goods after the demoulding.
The A of injection mould, the volume ratio of B two components are (0.1～10) after mixing: 1, be preferably 1: 1.Dicyclopentadiene and M
1Weight ratio be (200～1500): 1.Raw material dicyclopentadiene: WCl in A, the B two component mixed solutions
6=(200～1500): 1 (weight ratio) is preferably (250～400): 1 (weight ratio).Raw material dicyclopentadiene: aluminium diethyl monochloride=(100～500): 1 (weight ratio) is preferably (200～300): 1 (weight ratio).
The double-metal composite catalyst and the compound aluminum alkyls zinc halogenide activator that adopt the present invention to propose, the reaction injection molding technology is adopted in the polymerization of dicyclopentadiene, make not enhanced polydicyclopentadiene product by above-mentioned preparation method, the polymerisation conversion of dicyclopentadiene＞99%, the about 1.06g/cm of proportion
3, simply supported beam notched Izod impact strength＞40kgfcm/cm
2, bending elastic modulus＞1800MPa, heat-drawn wire＞60 ℃.
Adopt the preparation method of polydicyclopentadiene of the present invention, the catalyst system of double-metal composite catalyst that provides and compound aluminum alkyls zinc halogenide activator is low to the purity requirement of raw material dicyclopentadiene, can allow purity＞97% of raw material dicyclopentadiene, and former patent requires all＞99%.The polymerisation conversion height, the polymerisation conversion of former patent report generally is 90～95%, and polymerisation conversion of the present invention is about 98%, reaches as high as 99.6%.Because lower to the purity requirement of raw material dicyclopentadiene, thus be easy to controlled polymerization speed, but operating restraint is broadened, and the raw material separation requirement also reduced, thereby reduced the production cost of polydicyclopentadiene, simplified technological process, better results relatively.And because the raising of the polymerization degree, the unconverted monomer residual quantity is reduced, therefore goods almost do not have stink, and the degree of crosslinking height, and the mechanical property of polymkeric substance strengthens, good heat resistance, surface smoothness is good, and anti-impact and bending property improve, and need not to carry out aftertreatment, also expanded simultaneously the range of application of goods, as the parts of transportation means, the member of various device, the shell of electrical equipment etc.
Illustrate the present invention with embodiment below, but and do not mean that restriction the present invention.
Embodiment 1:
Preparation of catalysts: with 10 gram WCl
6Be dissolved in 200 milliliters of toluene solutions, change exsiccant over to and use in 1000 milliliters of there-necked flasks of nitrogen protection stirring; 4.1 gram p-tert-butylphenols are dissolved in 50 milliliters of toluene, also add in the there-necked flask, add 1 gram TiCl again
4, heat temperature raising to 90～100 ℃ make its backflow, react 16～20 hours, and the tail gas water absorbs, and reaction finishes postcooling, and material is transferred in the container, makes 0.1NWCl
6Phenol liquid.
The preparation of A component: with 0.467 milliliter of 36.72 milliliters of the catalyzer, the dicyclopentadiene that make 52.85 milliliters (dicyclopentadiene purity＞97%), benzyl acetonitrile, under nitrogen protection, mix, make 0.0408N tungsten/phenol and titanium/phenol solution.
The preparation of B component: with 11 milliliters of aluminium diethyl monochlorides, 0.8 milliliter of zinc ethyl, 86 milliliters of dicyclopentadiene (dicyclopentadiene purity＞97%), under nitrogen protection, mix, make the compound mixed solution of 0.97N aluminium diethyl monochloride-zinc ethyl.
Aggregation test: under nitrogen protection, feed temperature is controlled at 25～32 ℃, adds 0.54 milliliter of B component; 9.67 milliliters of dicyclopentadiene (dicyclopentadiene purity＞97%), 0.139 milliliter of polymerization time conditioning agent diethylene glycol dimethyl ether, 2.24 milliliters of A components; add successively in the polymerization Glass Containers; vigorous stirring, 70 ℃ of polymerization mould temperature are injected mould; heating at short notice heats up; aggregate into not flow solids, the cooling natural demoulding in back makes sample.The results are shown in table.
Embodiment 2～4:
Process of the test is with embodiment 1.Catalyzer is by not containing TiCl in the A component of embodiment 2
4Make.Embodiment 3 is with zinc ethyl cancellation in the B component.Embodiment 4 is with TiCl in A, the B component
4Cancel with zinc ethyl.The results are shown in table.Table one unit: milliliter
Embodiment 1 embodiment 2 embodiment 3 embodiment 4DCPD 84.56 84.56 84.56 84.56WCl
6/ phenol 0.0912 0.0912 0.0912 0.0912TiCl
4/ phenol 0.0192/0.0192/aluminium diethyl monochloride 0.489 0.489 0.489 0.489 zinc ethyl 0.0367 0.0367 // benzyl acetonitrile 0.1 0.1 0.1 0.1 diethylene glycol dimethyl ethers 0.978 0.978 0.978 0.978t
s(s) 74 72 71 75t
Max(s) 80 82 75 82T
Max(℃) 128 130 122 167P (%), 99.5 95 99.6 94.1t
s: A, B two components mix back gel time (s) t
Max: A, B two components are mixed to top temperature time (s) T
Max: top temperature after A, the B two component mixed polymerizations (℃) P: dicyclopentadiene transformation efficiency (%)
Embodiment 5～10;
Process of the test is only replaced polymerization time conditioning agent diethylene glycol dimethyl ether among the embodiment 1 respectively with embodiment 1 by other polymerization time conditioning agent.Add tetrahydrofuran (THF) among the embodiment 5.Add dibutyl ethylene glycol ether among the embodiment 6.Add n-butyl ether among the embodiment 7.Add isopropyl ether among the embodiment 8.Add methyl ethyl diketone among the embodiment 9.Add ethyl benzoate among the embodiment 10.Polymerization time conditioning agent in the test: aluminium diethyl monochloride=2: 1 (mol ratio), 25 ℃ of material temperature, 70 ℃ of mould temperature.The results are shown in table two.Table two unit: milliliter
Embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 embodiment 10 embodiment 1DCPD 84.56 84.56 84.56 84.56 84.56 84.56 84.56WCl
6/ phenol 0.0912 0.0912 0.0912 0.0912 0.0912 0.0912 0.0912TiCl
4/ phenol 0.0192 0.0192 0.0192 0.0192 0.0192 0.0192 0.0192 aluminium diethyl monochlorides 0.489 0.489 0.489 0.489 0.489 0.489 0.489 diethyl zinc 0.0367 0.0367 0.0367 0.0367 0.0367 0.0367 0.0367 benzyl acetonitriles 0.1 0.1 0.1 0.1 0.1 0.1 0.1 oxolanes 0.978 dibutyl ethylene glycol ether 0.978 n-butyl ether 0.978 isopropyl ether 0.978 acetylacetone,2,4-pentanedione 0.978 ethyl benzoate 0.978 diethylene glycol dimethyl ether 0.978ts(s) do not gather 118 45 30 poly-63 74t
Max(s) 126 64 53 82 80T
Max(℃) 132 143 122 138 128P (%), 99.3 98.7 99.1 98.8 99.5t
s: A, B two components mix back gel time (s) t
Max: A, B two components are mixed to top temperature time (s) T
Max: top temperature after A, the B two component mixed polymerizations (℃) P: dicyclopentadiene transformation efficiency (%)
Embodiment 11～14:
Process of the test is with embodiment 1.Embodiment 11 changes 9.67 milliliters of raw material dicyclopentadiene into 6.86 milliliters.Embodiment 12 changes 9.67 milliliters of raw material dicyclopentadiene into 10.57 milliliters.Embodiment 13 changes 9.67 milliliters of raw material dicyclopentadiene into 21.14 milliliters.Embodiment 14 changes 9.67 milliliters of raw material dicyclopentadiene into 47.65 milliliters.Dicyclopentadiene purity＞97%.25 ℃ of material temperature, 70 ℃ of mould temperature, the polymerization time conditioning agent is a diethylene glycol dimethyl ether, the polymerization time conditioning agent: aluminium diethyl monochloride=2: 1 (mol ratio).Test-results is listed in table three.Table three unit: milliliter
Embodiment 11 embodiment 12 embodiment 13 embodiment 14 embodiment 1DCPD 63.84 91.2 169.2 364.8 84.56WCl
6/ phenol 0.0912 0.00912 0.0912 0.0912 0.0912TiCl
4/ phenol 0.0192 0.0192 0.0192 0.0192 0.0192 aluminium diethyl monochlorides 0.489 0.489 0.489 0.489 0.489 diethyl zinc 0.0367 0.0367 0.0367 0.0367 0.0367 benzyl acetonitriles 0.1 0.1 0.1 0.1 0.1DCPD/W 700 1,000 2,000 4,000 927 diethylene glycol dimethyl ethers 0.978 0.978 0.978 0.978 0.978tMax(s) 68 83 545 gel 80T
Max(℃) 131 124 122 128 simply supported beam notched Izod impact strength 17.5 43.2 41.4 35.8
(kgf.cm/cm
2) bending elastic modulus (MPa) 1,811 2,035 2,076 2017 heat-drawn wires (℃) 82.6 84.3 84.3 82.3P (%), 97.8 99.2 99.1 99.5t
Max: A, B two components are mixed to top temperature time (s) T
Max: top temperature after A, the B two component mixed polymerizations (℃) P: dicyclopentadiene transformation efficiency (%)
Embodiment 15～19:
Process of the test is with embodiment 1.Embodiment 15 changes 0.54 milliliter of B component into 0.40 milliliter.Embodiment 16 changes 0.54 milliliter of B component into 0.599 milliliter, and embodiment 17 changes 0.54 milliliter of B component into 0.699 milliliter, and embodiment 18 changes 0.54 milliliter of B component into 0.998 milliliter, and embodiment 19 changes 0.54 milliliter of B component into 1.996 milliliters.25 ℃ of material temperature, 70 ℃ of mould temperature, the polymerization time conditioning agent is a diethylene glycol dimethyl ether, the polymerization time conditioning agent: aluminium diethyl monochloride=2: 1 (mol ratio).Test-results is listed in table four.Table four unit: milliliter
Embodiment 15 embodiment 16 embodiment 17 embodiment 18 embodiment 19 embodiment 1DCPD 84.56 84.56 84.56 84.56 84.56 84.56WCl
6/ phenol 0.0912 0.0912 0.0912 0.0912 0.0912 0.0912TiCl
4/ phenol 0.0192 0.0192 0.0192 0.0192 0.0192 0.0192 aluminium diethyl monochlorides 0.365 0.547 0.638 0.912 1.824 0.489 diethyl zinc 0.0274 0.0411 0.0479 0.0684 0.137 0.0367 benzyl acetonitriles 0.1 0.1 0.1 0.1 0.1 0.1 diethylene glycol dimethyl ethers 0.73 1.094 1.276 1.824 3.648 0.978Al/W 467 10 20 5.36tMax(s) 110 73 69 56 40 80T
Max(℃) 143 122 120 91 77 128 simply supported beam notched Izod impact strength, 24.5 42.6 41.9 34.5 17.6 35.8 (kgf.cm/cm
2) bending elastic modulus (MPa) 1,685 2,092 2,104 1,892 2,200 2017 heat-drawn wires (℃) 84.6 85.3 87.6 82.8 88.4 82.3P (%), 97.4 99.4 99.5 98.1 96.2 99.5t
Max: A, B two components are mixed to top temperature time (s) T
Max: top temperature after A, the B two component mixed polymerizations (℃) P: dicyclopentadiene transformation efficiency (%)
Embodiment 20～23:
Process of the test is with embodiment 1.Embodiment 20 reduces one times with the polymerization time conditioning agent, promptly adds 0.0695 milliliter.Embodiment 21 doubles the polymerization time conditioning agent, promptly adds 0.278 milliliter.Embodiment 22 increases by 1.5 times with the polymerization time conditioning agent, promptly adds 0.3475 milliliter.Embodiment 23 increases by 500 the polymerization time conditioning agent, promptly adds 0.695 milliliter.25 ℃ of material temperature, 70 ℃ of mould temperature.Test-results is listed in table five.
Table five unit: milliliter
Embodiment 20 embodiment 21 embodiment 22 embodiment 23 embodiment 1DCPD 84.56 84.56 84.56 84.56 84.56WCl
6/ phenol 0.0912 0.0912 0.0192 0.0912 0.0912TiCl
4/ phenol 0.0192 0.0192 0.0192 0.0192 0.0192 aluminium diethyl monochlorides 0.489 0.489 0.489 0.489 0.489 diethyl zinc 0.0367 0.0367 0.0367 0.0367 0.0367 benzyl acetonitriles 0.1 0.1 0.1 0.1 0.1 diethylene glycol dimethyl ethers 0.489 1.956 2.445 4.89 0.978 ether/aluminium diethyl monochloride 145 10 2tMax(s) 46 114 124 440 80T
Max(℃) 139 120 119 104 128 simply supported beam notched Izod impact strength, 40.5 34.4 35.1 21.5 35.8 (kgf.cm/cm
2) bending elastic modulus (Pa) 2,230 2,410 2,670 1,819 2017 heat-drawn wires (℃) 85.4 83.8 84.1 80.4 82.3P (%), 99.2 98.4 98.5 96.4 99.5t
Max: A, B two components are mixed to top temperature time (s) T
Max: top temperature after A, the B two component mixed polymerizations (℃) P: dicyclopentadiene transformation efficiency (%)
Embodiment 24～25:
Process of the test is with embodiment 1.Embodiment 24 changes the A component of preparation into catalyzer 36.72 milliliters, changes dicyclopentadiene (dicyclopentadiene purity＞97%) into 148.85 milliliters for 85 milliliters in the preparation of B component, and other is constant.Embodiment 25 is in the preparation of A component, and dicyclopentadiene (dicyclopentadiene purity＞97%) changes 148.85 milliliters into for 52.85 milliliters, cancels dicyclopentadiene in the preparation of B component.Test-results is listed in table six.
Table six unit: milliliter
Embodiment 24 embodiment 25 embodiment 1DCPD 148.56 148.56 84.56WCl
6/ phenol 0.0912 0.0912 0.0192TiCl
4/ phenol 0.0192 0.0192 0.0192 aluminium diethyl monochlorides 0.489 0.489 0.489 zinc ethyl 0.0367 0.0367 0.0367 benzyl acetonitriles/0.1 0.1 diethylene glycol dimethyl ethers, 0.978 0.978 0.978 ether/aluminium diethyl monochloride 22 2t
Max(s) 78 79 80T
Max(℃) 126 127 128 simply supported beam notched Izod impact strength, 36.0 35.9 35.8 (kgf.cm/cm
2) bending elastic modulus (MPa) 2,010 2,008 2017 heat-drawn wires (℃) 81 83 82.3P (%), 99.4 99.3 99.5t
Max: A, B two components are mixed to top temperature time (s) T
Max: top temperature after A, the B two component mixed polymerizations (℃) P: dicyclopentadiene transformation efficiency (%)
Claims (8)
1, a kind of preparation method of polydicyclopentadiene is characterized in that:
1. halogenide, transition metal halide, solvent toluene and the solubility promoter with raw material tungsten or molybdenum or tantalum joins in the usefulness there-necked flask of nitrogen protection that has reflux condensation mode, stirring, heating system together; make as shown in the formula described double-metal composite catalyst 60～150 ℃ of reactions
M
1(OAr
1)
n1·M
2(OAr
2)
n2·X
n3
In the formula: M
1Be a kind of in tungsten, molybdenum, the tantalum,
M
2Be a kind of in titanium, vanadium, the zirconium,
X is a halogen,
Ar
1And Ar
2Be a kind of in alkyl, cycloalkyl, aromatic base, the aralkyl,
N1 is 0～6, and n2 is 0～4, and n3 is 1～6, the halogenide of tungsten or molybdenum or tantalum: transition metal halide: solvent toluene: solubility promoter=1: (0.5～2): (4～8): (0.2～2) (weight ratio), M
1With M
2Weight ratio be (0.2～2.5): 1, described solubility promoter is a kind of in butanols, tertiary amyl alcohol, phenol, the p-tert-butylphenol,
2. above-mentioned double-metal composite catalyst mixes into the A component with dicyclopentadiene with stablizer in the there-necked flask with nitrogen protection; double-metal composite catalyst: dicyclopentadiene: stablizer: additive=1: (0～1500): (0.001～0.01): (10～100) (weight ratio); described stablizer is a kind of in benzyl formonitrile HCN, benzyl acetonitrile, methyl ethyl diketone, the tetrahydrofuran (THF); described additive is meant fire retardant, softening agent, tackifier, filler, pigment
3. with dicyclopentadiene; activator; polymerization time conditioning agent and additive are with nitrogen protection; and temperature is to mix into the B component in 30～40 ℃ the there-necked flask; dicyclopentadiene: activator: polymerization time conditioning agent: additive=(0～500): 1: (10～100): (1～100) (weight ratio); described activator is compound aluminum alkyls zinc halogenide; it can be triethyl aluminum; aluminium diethyl monochloride; ethyl aluminum dichloride; a kind of and zinc ethyl in the iodine aluminium triethyl; chloroethyl zinc; a kind of mixture that matches in the iodine zinc ethyl; described polymerization time conditioning agent is a diethylene glycol dimethyl ether; a kind of or both mixtures of dibutyl ethylene glycol ether; described additive is meant fire retardant; softening agent; tackifier; filler; pigment
4. have at least in the component in A component and B component and A, the B component and contain dicyclopentadiene, adopt the reaction injection molding polymerization, 20～40 ℃ of material temperature, 20～100 ℃ of polymerization mould temperature.
2, according to the preparation method of the described polydicyclopentadiene of claim 1, it is characterized in that: M in the double-metal composite catalyst
1Be tungsten, M
2It is titanium.
3, according to the preparation method of the described polydicyclopentadiene of claim 1, it is characterized in that: compound aluminum alkyls zinc halogenide is aluminium diethyl monochloride and zinc ethyl, and the weight ratio of aluminium diethyl monochloride and zinc ethyl is (10～25): 1.
4, according to the preparation method of the described polydicyclopentadiene of claim 1, it is characterized in that: the polymerization time conditioning agent is diethylene glycol dimethyl ether and dibutyl ethylene glycol ether, and the weight ratio of diethylene glycol dimethyl ether and dibutyl ethylene glycol ether is (0.1～10): 1.
5, according to the preparation method of claim 1 or 2 described dicyclopentadiene, it is characterized in that: M
1With M
2Weight ratio be (0.5～2): 1.
6, according to the preparation method of the described polydicyclopentadiene of claim 1, it is characterized in that: dicyclopentadiene and M
1Weight ratio be (200～1500): 1.
7, according to the preparation method of the described polydicyclopentadiene of claim 1, it is characterized in that: the weight ratio of dicyclopentadiene and aluminium diethyl monochloride is (100～500): 1.
8, according to the preparation method of the described polydicyclopentadiene of claim 1, it is characterized in that: the weight ratio of polymerization time conditioning agent and aluminium diethyl monochloride is (10～100): 1.
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|---|---|---|---|
| CN97106423A CN1084340C (en) | 1997-05-19 | 1997-05-19 | Preparation of polydicyclopentadiene |
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| CN1084340C true CN1084340C (en) | 2002-05-08 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205344B (en) * | 2006-12-19 | 2010-04-14 | 河南科技大学 | Preparation of polydicyclopentadiene/montmorillonite nano composite material |
| CN1995081B (en) * | 2006-12-27 | 2011-07-06 | 上海新天和树脂有限公司 | Double-component catalyst system for dicyclopentadiene loop-opening, replacement and polymerization and its polymerization process |
| CN101597351B (en) * | 2009-06-25 | 2011-09-28 | 河南科技大学 | Preparation method of polydicyclopentadiene/rubber in-situ polymerization blending composite material |
| CN101792505B (en) * | 2010-01-13 | 2012-06-06 | 黎明化工研究院 | Halogen-free flame-retardant dicyclopentadiene material and preparation method thereof |
| CN101891931B (en) * | 2010-07-08 | 2011-12-21 | 河南科技大学 | Polydicyclopentadiene/ethylene copolymer in-situ polymerization blend composite and preparation method thereof |
| CN102558731B (en) * | 2010-12-15 | 2014-04-23 | 河南科技大学 | Polydicyclopentadiene/polystyrene interpenetrating polymer network and preparation method thereof |
| CN102675511B (en) * | 2011-03-07 | 2014-09-10 | 河南科技大学 | Wear-resistant poly(dicyclopentadiene) nanocomposite and preparation method thereof |
| CN103665700B (en) * | 2013-08-27 | 2015-10-07 | 河南科技大学 | A kind of Polydicyclopentadiencomposite composite material and preparation method thereof |
| CN104497185A (en) * | 2014-12-26 | 2015-04-08 | 中国蓝星（集团）股份有限公司 | Composition for reaction injection molding and application thereof |
| CN107200803B (en) * | 2016-03-17 | 2019-11-12 | 中国石油化工股份有限公司 | A method of catalyst system and cycloolefin ring-opening polymerisation for cycloolefin ring-opening polymerisation |
| CN106479102A (en) * | 2016-08-31 | 2017-03-08 | 湖南华强电气股份有限公司 | Car air-conditioner DCPD composite cover plate |
| CN106398075A (en) * | 2016-08-31 | 2017-02-15 | 湖南华强电气股份有限公司 | DCPD composite material for vehicle air-conditioner base |
| CN112679639B (en) * | 2020-12-23 | 2022-08-26 | 广东新华粤石化集团股份公司 | Cycloolefin polymer and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4400340A (en) * | 1982-01-25 | 1983-08-23 | Hercules Incorporated | Method for making a dicyclopentadiene thermoset polymer |
| CN87103860A (en) * | 1986-05-09 | 1988-02-24 | 赫尔克里斯有限公司 | Be used to gather the phosphonium flame retardant composition of (dicyclopentadiene) reaction injection moulding |
| US5082909A (en) * | 1990-10-12 | 1992-01-21 | Hercules Incorporated | Pure tungsten oxyphenolate complexes as DCPD polymerization catalysts |
-
1997
- 1997-05-19 CN CN97106423A patent/CN1084340C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4400340A (en) * | 1982-01-25 | 1983-08-23 | Hercules Incorporated | Method for making a dicyclopentadiene thermoset polymer |
| CN87103860A (en) * | 1986-05-09 | 1988-02-24 | 赫尔克里斯有限公司 | Be used to gather the phosphonium flame retardant composition of (dicyclopentadiene) reaction injection moulding |
| US5082909A (en) * | 1990-10-12 | 1992-01-21 | Hercules Incorporated | Pure tungsten oxyphenolate complexes as DCPD polymerization catalysts |
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