CN1178804A - Preparation method of dicyclopentadiene modified unsaturated polyester resin - Google Patents
Preparation method of dicyclopentadiene modified unsaturated polyester resin Download PDFInfo
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- CN1178804A CN1178804A CN 96119856 CN96119856A CN1178804A CN 1178804 A CN1178804 A CN 1178804A CN 96119856 CN96119856 CN 96119856 CN 96119856 A CN96119856 A CN 96119856A CN 1178804 A CN1178804 A CN 1178804A
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- acid
- dicyclopentadiene
- unsaturated polyester
- polyester resin
- dcpd
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- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 title claims abstract description 57
- 229920006337 unsaturated polyester resin Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000007259 addition reaction Methods 0.000 claims abstract description 13
- 238000004132 cross linking Methods 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 12
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 230000032050 esterification Effects 0.000 claims description 28
- 238000005886 esterification reaction Methods 0.000 claims description 28
- 150000008065 acid anhydrides Chemical class 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 11
- 229920006305 unsaturated polyester Polymers 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 10
- 238000010790 dilution Methods 0.000 claims description 8
- 239000012895 dilution Substances 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 4
- LDUKQFUHJZHLRC-UHFFFAOYSA-N cydecanol Chemical compound C12C=CCC2C2CC(O)C1C2 LDUKQFUHJZHLRC-UHFFFAOYSA-N 0.000 claims description 4
- 150000007520 diprotic acids Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 2
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims 2
- 230000020477 pH reduction Effects 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000007787 solid Substances 0.000 abstract description 4
- 150000008064 anhydrides Chemical class 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 abstract 4
- 238000007865 diluting Methods 0.000 abstract 1
- 150000002009 diols Chemical class 0.000 abstract 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 15
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 8
- 150000001991 dicarboxylic acids Chemical class 0.000 description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- -1 alcohol ester Chemical class 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000005070 sampling Methods 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 239000001530 fumaric acid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229940059574 pentaerithrityl Drugs 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical class CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 2
- 238000005698 Diels-Alder reaction Methods 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical group C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- DJKGDNKYTKCJKD-UHFFFAOYSA-N chlorendic acid Chemical compound ClC1=C(Cl)C2(Cl)C(C(=O)O)C(C(O)=O)C1(Cl)C2(Cl)Cl DJKGDNKYTKCJKD-UHFFFAOYSA-N 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical class COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
A process for preparing dicyclopentadiene modified unsaturated polyester resin (DCPD modified UPR) includes addition reaction of dicyclopentadiene, esterifying reaction of diacid (or anhydride) and diol, polycondensation reaction and diluting by adding vinyl cross-linking monomer. The method has low requirement on the purity of the DCPD, low production cost, good economic benefit, stable control of process conditions and universal production equipment with the equipment in the prior art. The DCPD modified UPR has low viscosity, high solid content and low product shrinkage. Compared with the existing general resin, the DCPD modified UPR has the advantages of good heat resistance, good water resistance and chemical corrosion resistance, no lower mechanical property than the existing general resin, and wide application.
Description
The present invention relates to a kind of preparation method of dicyclopentadiene (DCPD) modified unsaturated polyester resin (UPR).The linear polymer that unsaturated polyester resin is normally formed by unsaturated dicarboxylic acid (or acid anhydride) and saturated dicarboxylic acid (or acid anhydride) and dibasic alcohol ester, polycondensation adds vinyl interlinkage monomer such as vinylbenzene again and makes.This resin adopts various working methods such as hand paste, injection, mold pressing, winding etc. to can be made into various glass fiber reinforced plastics products under effects such as solidifying agent, promotor.
DCPD is ethylene industry by-product cracking C
5Cut separates the hydrocarbons that obtains, because the chemically reactive height is the raw material of petroleum resin and multiple fine chemicals.Have now found that, DCPD introduced the UPR main chain UPR performance is improved that, resistance to chemical attack heat-resisting, water-fast as it and mechanical mechanics property all are better than universal UPR.
DCPD introduces the issuable chemical reaction of UPR following 3 kinds.
Wherein (1) is etherification reaction, consumes alcohol; (2) be esterification, consumption acids; (3) be the addition reaction of Diels-Alder diene, consume two keys of unsaturated dibasic acid.Just formed the multiple preparation method of DCPD modification UPR just because of these reactions.
With regard to the present state of the art, the method for preparing DCPD modification UPR mainly contains initial method, blocking method, sour selectivity catalysis method, addition hydrolysis method etc.Promptly adopt initial legal system to be equipped with DCPD modification UPR as United States Patent (USP) 4029848, Chinese patent CN1070657A promptly adopts blocking method to prepare DCPD modification UPR, United States Patent (USP) 4246367 promptly adopts the addition hydrolysis method to prepare the DCPD modification UPR of high DCPD content, its advantage is the active high of goods and vinyl monomer copolymerization, air-drying property is good, and is low to the DCPD purity requirement simultaneously.The method that to the effect for preparing high-content dicyclopentadiene (DCPD) unsaturated polyester resin of USP4246367, dicyclopentadiene content reaches 60.11% (weight percent), the method preparation process was divided into for 2 steps, the first step is that multi-anhydride, water and DCPD react time enough at 90～150 ℃, generates the toxilic acid half ester (half ester content is 25%mol at least) of DCPD alcohol.Proportioning raw materials is a multi-anhydride: water: DCPD is 100 (maleic anhydrides at least 25%): the water of capacity: 50～200 (moles); The mixture that second step added polyvalent alcohol and polyvalent alcohol carries out esterification, can add C during polycondensation if desired
8-C
22Lipid acid and Shanbo's alcohol, the proportioning of multi-anhydride and polyvalent alcohol is 100: 25～100 (moles).Measure the molecular weight of acid number control reaction, the final acid number of unsaturated polyester is＜55mgKOH/g.
The object of the present invention is to provide the preparation method of a kind of dicyclopentadiene (DCPD) modified unsaturated polyester resin (UPR).This method is low to the DCPD purity requirement, and production cost is low, and is good in economic efficiency.
Method of the present invention comprises the esterification of addition reaction, diprotic acid (or acid anhydride) and the dibasic alcohol of dicyclopentadiene, polycondensation and four steps of adding vinyl cross-linking monomer dilution.
The addition reaction of wherein said dicyclopentadiene generates the half ester of dicyclopentadiene alcohol for unsaturated dibasic acid or acid anhydride, water and dicyclopentadiene were carried out addition reaction 2～5 hours normal pressure, 60～140 ℃.Reinforced proportioning is unsaturated dibasic acid or acid anhydride: dicyclopentadiene is 100: 20～100 (mol ratios).
The esterification of wherein said diprotic acid (or acid anhydride) and dibasic alcohol was carried out esterification 3～8 hours for adding monounsaturated dicarboxylic acid or acid anhydride and dibasic alcohol and a small amount of stopper in the system after addition reaction, heating up at 160～210 ℃.Reinforced proportioning is: unsaturated dibasic acid or acid anhydride, and comprise the dicyclopentadiene alcohol half ester of unsaturated dibasic acid: monounsaturated dicarboxylic acid or acid anhydride: dibasic alcohol is 100: 0～100: 50～200 (mol ratios), and the acid number of esterification products is 50～60mgKOH/g;
Wherein said polycondensation is for to maintain the temperature at 200～300 ℃ with the system after the esterification, add vacuum gradually until 0.094MPa, carried out polycondensation 1～2 hour, generate unsaturated polyester, the mensuration acid number is 10～40mgKOH/g, finishes reaction and is cooled to 90 ℃.
Wherein said adding vinyl cross-linking monomer dilution is that the reactant after the polycondensation is added vinyl cross-linking monomer such as vinylbenzene at 90 ℃, ratio is unsaturated polyester 65～75% (mass percent): vinyl cross-linking monomer 35～25% (quality percentage composition ratio), reduce to normal temperature after stirring, filter and promptly make dicyclic pentylene modified unsaturated polyester resin.
Wherein said dicyclopentadiene is used ethylene industry by-product cracking C
5The isolating technical grade dicyclopentadiene of cut, content 〉=78% (m) needn't use highly purified dicyclopentadiene.
Now the preparation method with DCPD modification UPR is described in detail as follows:
(1) DCPD addition
With unsaturated dibasic acid (or acid anhydride), have usually to add in maleic anhydride, the fumaric acid to be less than the stoichiometric water of acid anhydrides and to react and generate acid, control reaction temperature slowly adds DCPD at 60～140 ℃, reacts under nitrogen protection 2～5 hours.This moment, proportioning raw materials was that unsaturated dibasic acid (or acid anhydride) is 100: 20～100 (moles) with the DCPD ratio, and reaction product is the toxilic acid half ester or the fumaric acid half ester of DCPD alcohol.
(2) esterification
In the adduct of (1), add monounsaturated dicarboxylic acid or acid anhydride (Tetra hydro Phthalic anhydride (PA), terephthalic acid (TPA), m-phthalic acid (MPA), oxalic acid, tetrahydrophthalic anhydride, HET acid etc. are arranged usually) and dibasic alcohol (ethylene glycol (EG), propylene glycol (PG), Diethylene Glycol (DEG), neopentyl glycol etc. are arranged usually) in proportion, add hydroquinone of polymerization retarder 0.01%, 160～210 ℃ of control reaction temperature, carried out esterification 3～8 hours, the water that constantly removes the esterification generation is till nothing distillates.This moment, the product acid number was 50～60mgKOH/g.Unsaturated dibasic acid (comprising half ester) is 100: 0～100: 50～200 (moles) with the proportioning of monounsaturated dicarboxylic acid (or acid anhydride) and dibasic alcohol.
(3) polycondensation
(2) esterification products is added vacuum gradually until 0.094MPa, and keep 200～205 ℃ of temperature of reaction, carried out polycondensation 1～2 hour, obtain unsaturated polyester, acid number is 10～40mgKOH/g, stops vacuum and is cooled to 90 ℃.
(4) dilution
With the unsaturated polyester of (3) of 65～75% (mass percents) and vinyl cross-linking monomer (vinylbenzene, αJia Jibenyixi, Vinyl toluene, methyl methacrylate, n-butyl acrylate, phthalic acid diallyl etc. are arranged usually) 30～25% (quality percentage this), carry out thorough mixing, promptly get product after the filtration.
The present invention and the something in common of USP4246367 are that DCPD and acid anhydrides, the capable principle of carrying out addition reaction of water are identical, the processing step of two-step approach also is identical, but actual conditions condition, proportioning raw materials and reaction content are all inequality, and difference is tangible; Following 4 points are specifically arranged:
(1) temperature of reaction of the first step multi-anhydride, water and DCPD is 90～150 ℃ among the USP4246367, it is the high temperature addition reaction, and temperature of reaction of the present invention is 60～140 ℃, belong to the multi-anhydride of participating in the first step reaction among the low temperature addition reaction USP4246367 undersaturated maleic anhydride is not only arranged, also has saturated Tetra hydro Phthalic anhydride, require toxilic acid to be no less than 0.25% (mole), and have only unsaturated acid or anhydride such as cis-butenedioic anhydride and fumaric acid to participate in the half ester reaction of the present invention, there is not saturated acid or anhydride to participate in.
(2) the second step esterification adds the mixture of polynary pure and mild polyvalent alcohol among the USP4246367, all having added tetramethylolmethane among all embodiment increases the degree of crosslinking and the molecular weight of unsaturated polyester, it is one of main protection content of this patent that polyvalent alcohol such as tetramethylolmethane esterification are adopted in this explanation, because this patent will prepare the unsaturated polyester of the high-content DCPD molecular weight of just must trying every possible means to increase; The present invention is used is dibasic alcohol, as propylene glycol, ethylene glycol, Diethylene Glycol, neopentyl glycol etc., increases degree of crosslinking and molecular weight without polyvalent alcohol such as tetramethylolmethane.The present invention adds the mixture of saturated dibasic ester (or acid anhydride) and dibasic alcohol and dibasic alcohol in esterification, this illustrates the esterification principle of esterification of the present invention and USP4246367 and acts on incomplete same.
Used polyvalent alcohol mole proportioning difference in the esterification, acid anhydrides and polyvalent alcohol proportioning are 100: 25～100 (moles) among the USP4246367, unsaturated acid anhydride of the present invention: saturated acid anhydrides: dibasic alcohol is 100: 0～100: 50～100 (moles).
(3) do not have this step of polycondensation among the USP4246367, only control the final acid number＜55mgKOH/g of the second step esterification.Acid number is 50～60mgKOH/g after the esterification of the present invention, and the unsaturated polyester acid number is too high, need carry out polycondensation 1～2 hour.Final acid number is 10～40mgKOH/G.
(4) DCPD that is adopted among the USP4246367 is the product of EXXON company, wherein contains DCPD59% (weight percent), the dipolymer 25% (weight percent) of methyl DCPD, and all the other are hydrocarbons.The DCPD that the present invention adopts is ethylene industry byproduct cracking C
5The technical grade DCPD that cut is separating obtained, content 〉=78% does not have methyl DCPD dipolymer, and all the other are hydrocarbons.
The present invention adopts the way of CONTROL PROCESS condition, controlled temperature and proportioning to make DCPD enter the UPR main chain, avoid the generation of Diels-Alder reaction, add monounsaturated dicarboxylic acid (or acid anhydride) in the esterification simultaneously and carry out polycondensation to increase molecular weight, obtain the unsaturated polyester of better performances, and do not increase molecular weight by multi-functional alcohol (as tetramethylolmethane) and macromolecular dibasic alcohol (as the derivative of dihydroxyphenyl propane and dihydroxyphenyl propane).
Method of the present invention and the product characteristics that is provided thereof are:
1. low to the DCPD purity requirement, production cost is low, and is good in economic efficiency.
2. preparation method's proceed step by step, as comprise addition, esterification, polycondensation, four steps of dilution, processing condition control steadily, production unit can with the Device-General of prior art.
That 3.DCPD the characteristics of modification UPR physicochemical property are viscosity is low (0.2～0.6Pa.S), solid content height (65～75%), its goods shrinking percentage low (＜1%).
4. its goods have good heat-resisting, water-fast, resistance to chemical corrosion.Mechanical mechanics property is not less than universal UPR.
5. resin has good adhesive power to glass fibre.Product surface smooth finish is good, and air-drying property is good.
Embodiment 1
1000ml four-hole round-bottomed flask, band thermometer, temperature probe, agitator, nitrogen ingress pipe and fractional column, and be furnished with condenser and overhead product receptor.In flask, drop into 196g cis-butenedioic anhydride and 38g water, start and stir, begin heating, when temperature rises to 60 ℃, slowly drip dicyclopentadiene 297g, after dicyclopentadiene dropwises, controlled temperature continues reaction 1 hour between 120～130 ℃, this moment, acid number temperature to 170 ℃ was carried out esterification, constantly distillated the water that reaction generates, and temperature also constantly rises.When the no distillate of reaction, at 205 ℃ of insulation half an hour and sampling and measuring acid number 50.1mgKOH/g.Holding temperature is constant, vacuumizes gradually to carry out polycondensation 1 hour, stops vacuum and cooling, sampling analysis acid number 27.2mgKOH/g.When temperature is reduced to 90 ℃, add 235g vinylbenzene and dilute, the viscosity that obtains resin is 0.32Pa.S, and acid number is 20.2mgKOH/g, and gelation time is 11Min30s, solid content 69%.
Embodiment 2
1000ml four-hole round-bottomed flask has thermometer, temperature control probe, agitator, nitrogen ingress pipe and fractional column, and is furnished with condenser and overhead product receptor.In flask, drop into 98g cis-butenedioic anhydride and 18g water, start and stir, begin heating, when temperature rises to 60 ℃, slowly add dicyclopentadiene 78g, controlled temperature is between 100-120 ℃, after dicyclopentadiene dropwised, insulation continued reaction 1 hour, at this moment acid number 231.3mgKOH/g.Add glycol ether 74.2g then, propylene glycol 47g, phthalic anhydride 74g and 0.04g Resorcinol slowly are warmed up to 180 ℃ and carry out esterification.Constantly distillate the water that reaction generates, temperature also constantly rises, when the reaction nothing is reserved liquid, at 200 ℃ of insulation half an hour and sampling and measuring acid number 55.7mgKOH/g.Keep temperature-resistant vacuumizing to carry out polycondensation 1.5 hours, stop vacuum and cooling, sampling analysis acid number 29.3mgKOH/g.When temperature drops to 90 ℃, add 156g vinylbenzene and dilute, the viscosity that obtains resin is 0.429Pa.S, and acid number is 18.9mgKOH/g, and gelation time is 8min10s, solid content 70%.
Embodiment 3
The 10000L reactor has agitator, temperature demonstration, fractional column.Drop into cis-butenedioic anhydride, fumaric acid and water at the reactor charging opening, startup is stirred and is heated up, and slowly adds dicyclopentadiene when temperature reaches 60 ℃, after the dicyclopentadiene adding finishes, temperature is controlled at and continues reaction 2 hours between 90～120 ℃, and the mensuration acid number is 251.6mgKOH/g.Add propylene glycol, glycol ether and Resorcinol then successively.Slowly be warmed up to 190 ℃ and carry out esterification, constantly distillate the water that generates in the reaction, stop vacuum, the sampling analysis acid number is 32.2mgKOH/g.Logical cooling water temperature when temperature is reduced to 120 ℃, is put into dilution still (the dilution still has added 270Kg vinylbenzene) by discharge valve with poly-unsaturated acid and is diluted.Obtaining resin is yellow transparent liquid, and its viscosity is 0.36Pa.S, and acid number is 20.2mgKOH/g, and gelation time is 13min17s.Proportioning raw materials sees Table 1, and the pour mass performance sees Table 2.
Table 1 proportioning of feeding in raw material: name (Kg) MolMA 165 1.68FA 84 0.72H that weigh
2O 30 1.67DCPD 185 1.20DEG 166 1.56PG 28 0.37Sty 270 2.60
Table 2 resin-cast body performance is: title index flexural strength MPa 75.5 heat-drawn wires ℃ 83.3 shrinking percentage %, 0.43 Ba Ke hardness 44
Claims (6)
1, a kind of method for preparing dicyclic pentylene modified unsaturated polyester resin, comprising the esterification of addition reaction, diprotic acid (or acid anhydride) and the dibasic alcohol of dicyclopentadiene, polycondensation and add four steps of vinyl cross-linking monomer dilution.
2, the described method for preparing dicyclic pentylene modified unsaturated polyester resin of claim 1, the addition reaction of wherein said dicyclopentadiene generates the half ester of dicyclopentadiene alcohol for unsaturated dibasic acid or acid anhydride, water and dicyclopentadiene were carried out addition reaction 2～5 hours normal pressure, 60～140 ℃; Reinforced proportioning is unsaturated dibasic acid or acid anhydride: dicyclopentadiene is 100: 20～100 (mol ratios).
3, the described method for preparing dicyclic pentylene modified unsaturated polyester resin of claim 1, the esterification of wherein said diprotic acid (or acid anhydride) and dibasic alcohol was carried out esterification 3～8 hours for adding monounsaturated dicarboxylic acid or acid anhydride and dibasic alcohol and a small amount of stopper in the system after addition reaction, heating up at 160～210 ℃; Reinforced proportioning is: unsaturated dibasic acid or acid anhydride, comprise the dicyclopentadiene alcohol half ester of unsaturated dibasic acid: monounsaturated dicarboxylic acid or acid anhydride: dibasic alcohol is 100: 0～100: 50～200 (mol ratios), the acid number 50～60mgKOH/G of esterification products.
4, the described method for preparing dicyclic pentylene modified unsaturated polyester resin of claim 1, wherein said polycondensation is for to maintain the temperature at 200～205 ℃ with the system behind the acidification reaction, add vacuum gradually until 0.094MPa, carried out polycondensation 1～2 hour, generate unsaturated polyester, the mensuration acid number is 10～40mgKOH/g, finishes reaction and is cooled to 90 ℃.
5, the described method for preparing dicyclic pentylene modified unsaturated polyester resin of claim 1, wherein said adding vinyl cross-linking monomer dilution is that the reactant after the polycondensation is added the vinyl cross-linking monomer at 90 ℃, ratio is unsaturated polyester 65～75 (mass percentage content): vinyl cross-linking monomer 35～25% (mass percentage content), reduce to normal temperature after stirring, filter and promptly make dicyclic pentylene modified unsaturated polyester resin.
6, according to the described method for preparing dicyclic pentylene modified unsaturated polyester resin of claim 1, wherein said dicyclopentadiene is used ethylene industry by-product cracking C
5The isolating technical grade dicyclopentadiene of cut, content 〉=78% (m).
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| CN96119856A CN1056388C (en) | 1996-10-03 | 1996-10-03 | Preparation method of dicyclopentadiene modified unsaturated polyester resin |
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| CN96119856A CN1056388C (en) | 1996-10-03 | 1996-10-03 | Preparation method of dicyclopentadiene modified unsaturated polyester resin |
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| CN1056388C CN1056388C (en) | 2000-09-13 |
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| US4029848A (en) * | 1976-01-21 | 1977-06-14 | The Dow Chemical Company | Unsaturated polyester resins containing a dicyclopentadiene concentrate |
| US4246367A (en) * | 1979-09-24 | 1981-01-20 | United States Steel Corporation | Dicyclopentadiene polyester resins |
| JPS6329773A (en) * | 1986-07-23 | 1988-02-08 | Canon Inc | Developing device |
| CN1034279C (en) * | 1992-03-07 | 1997-03-19 | 福州大学 | Method for preparaing dicyclc pentylene modified unsaturated polyester |
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