CN101230131B - Preparation method of thickened dicyclopentadiene unsaturated polyester resin - Google Patents
Preparation method of thickened dicyclopentadiene unsaturated polyester resin Download PDFInfo
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- CN101230131B CN101230131B CN2007100510485A CN200710051048A CN101230131B CN 101230131 B CN101230131 B CN 101230131B CN 2007100510485 A CN2007100510485 A CN 2007100510485A CN 200710051048 A CN200710051048 A CN 200710051048A CN 101230131 B CN101230131 B CN 101230131B
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- Prior art keywords
- unsaturated polyester
- polyester resin
- preparation
- thickenable
- terepthaloyl moietie
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- 229920006337 unsaturated polyester resin Polymers 0.000 title claims abstract description 34
- 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 24
- 238000002360 preparation method Methods 0.000 title claims description 22
- 239000002253 acid Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 6
- 238000010790 dilution Methods 0.000 claims abstract description 4
- 239000012895 dilution Substances 0.000 claims abstract description 4
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims description 20
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- BDKZHNJTLHOSDW-UHFFFAOYSA-N [Na].CC(O)=O Chemical compound [Na].CC(O)=O BDKZHNJTLHOSDW-UHFFFAOYSA-N 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 59
- 239000011347 resin Substances 0.000 abstract description 59
- 230000008719 thickening Effects 0.000 abstract description 30
- 238000000034 method Methods 0.000 abstract description 11
- 239000011159 matrix material Substances 0.000 abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 7
- 238000007259 addition reaction Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 229920006305 unsaturated polyester Polymers 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000001993 dienes Chemical class 0.000 abstract description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 2
- 150000008064 anhydrides Chemical class 0.000 abstract 1
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 239000003112 inhibitor Substances 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 238000007040 multi-step synthesis reaction Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 27
- 238000012360 testing method Methods 0.000 description 21
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- 150000007520 diprotic acids Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- -1 paratoluenesulfonic acid sodium salt Chemical class 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinyl group Chemical group C1(O)=CC(O)=CC=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical class [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical group OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- LFULEKSKNZEWOE-UHFFFAOYSA-N propanil Chemical compound CCC(=O)NC1=CC=C(Cl)C(Cl)=C1 LFULEKSKNZEWOE-UHFFFAOYSA-N 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
A method for preparing a thickened dicyclopentadiene unsaturated polyester resin is characterized by comprising the following steps: adding reaction raw materials of dibasic acid (anhydride) and deionized water into a reactor according to the molar ratio of 1: 1.0-1.2, heating to 100-140 ℃ and carrying out hydrolysis reaction for 0.5-1 h; dripping 0.4-0.8 mol of dicyclopentadiene at 110-180 ℃ to perform hydrogen ion shift addition reaction and diene addition reaction, and reacting at the temperature for 1-2 h; adding 0.3-0.7 mol of dihydric alcohol, a catalyst accounting for 0.07-0.30% of the total weight of the materials and a polymerization inhibitor accounting for 0.03-0.07% of the total weight of the materials, and gradually heating to 200-210 ℃ to perform polycondensation for 0.5-1 h; and (3) adding styrene for dilution after vacuum dehydration to obtain the product. The dicyclopentadiene unsaturated polyester resin synthesized by the multi-step synthesis method has thickening property, and the product is suitable for being used as matrix resin of unsaturated polyester molding compound.
Description
Technical field
The invention belongs to the preparation method of macromolecular compound, relate to a kind of preparation method of thickenable dicyclopentadiene unsaturated polyester resin, the resin of this method preparation is suitable for the matrix resin of making unsaturated polyester die plastic (SMC/BMC).
Background technology
Unsaturated polyester resin is a kind of thermosetting resin.The thermosetting material of pure unsaturated polyester resin, its physical strength is lower, generally adopts strongthener to process matrix material and uses.The unsaturated polyester resin that is widely used in matrix material now is O-phthalic acid type (being called for short adjacent benzene type), m-phthalic acid type (abbreviation metaphenylene), bisphenol A-type and vinyl ester type, halo unsaturated polyester resin basically, dicyclopentadiene type unsaturated polyester resin etc.
The Yang Kai of South China Science & Engineering University etc. has inquired into various influence factors of dicyclic pentylene modified unsaturated polyester resin synthetic and main technique condition thereof.When the ratio of the amount of cis-butenedioic anhydride and phthalic anhydride is 0.22; The ratio of the amount of NSC 7352 and total acid is 0.15; Catalyst levels is 0.24%; The vinylbenzene consumption is 30%～35%; The end-blocking temperature is controlled at 155 ℃; The addition time, the synthetic resin had good air-drying property when being 3h.This resin does not have thickening properties as the matrix resin of hand paste glass reinforced plastic.
Chinese patent ZL96119856.7 disclosed " a kind of preparation method of dicyclic pentylene modified unsaturated polyester resin " has introduced a kind of method for preparing dicyclic pentylene modified unsaturated polyester resin (DCPD modification UPR); Comprising the esterification of addition reaction, diprotic acid (or acid anhydride) and the divalent alcohol of NSC 7352, polycondensation with add four steps of vinyl cross-linking monomer dilution.This resin is water-fast, resistance to chemical corrosion good, but does not have thickening properties.
One Chinese patent application 200510026882.X disclosed " a kind of preparation method of dicyclic pentylene modified unsaturated polyester resin " has introduced the preparation method of a kind of dicyclic pentylene modified unsaturated polyester resin (DCPD modification UPR), and comprising: 1) unsaturated dicarboxylic acid anhydride, water and NSC 7352 carry out the DCPA that addition reaction obtains unsaturated dibasic acid in the presence of catalyzer.Catalyzer is the compsn of phosphoric acid and toluene sulfonic acide, and wherein the weight ratio of phosphoric acid and toluene sulfonic acide is 2～6: 1; 2) mixture that adds divalent alcohol and trivalent alcohol in the reaction system carries out polycondensation, and the acid number of reactant finishes to react after less than 50mgKOH/g, removes the water of generation in the reaction process; 3) reactant is cooled to 100 ℃～110 ℃, adds vinyl cross-linking monomer diluting reaction thing and adds stopper, promptly gets dicyclic pentylene modified unsaturated polyester resin after the mixing.The advantage of this invention product is that its goods of gained UPR have more excellent thermotolerance, and heat-drawn wire is higher than the state of the art of currently available products greater than 100 ℃.This resin is also stuck with paste the matrix resin of glass reinforced plastic as hand, do not have thickening properties equally.
Summary of the invention
It is poor that the object of the invention is intended to overcome the existing ubiquitous thickening property of dicyclopentadiene type unsaturated polyester resin; Can not satisfy the deficiency of unsaturated polyester die plastic request for utilization; Through multistep processes catalyzed reaction technology; Improve compound method and process, thereby but the preparation method of the dicyclopentadiene type unsaturated polyester resin of a kind of processing ease, constant product quality, the lower thickening of cost is provided.
Dicyclopentadiene type unsaturated polyester resin compound molecular weight of the present invention is high, and weight-average molecular weight reaches 2700～4500, Stability Analysis of Structures, and molecular structure is shown below:
In the formula:
R
1, R
3For: HO-CH
2-CH
2-; HO-CH
2-CH
2-O-CH
2-CH
2-;
R
2For :-CH
2-CH
2-O-CH
2-CH
2-;-CH
2-CH
2-;
N is the integer more than or equal to 2.
Content of the present invention is: a kind of preparation method of thickenable dicyclopentadiene unsaturated polyester resin; It is characterized in that comprising the following steps: with the reaction raw materials diprotic acid or/and dibasic acid anhydride and deionized water (or claiming softening water) the mole proportioning amount of getting according to 1: 1.0～1.2 joins in the reactor drum, be warming up to 100 ℃～140 ℃ and be hydrolyzed and react 0.5～1h; Drip 0.4～0.8mol NSC 7352 in 110 ℃～180 ℃ and carry out hydrogen ion displacement addition reaction and diene addition reaction, after dripping, under this temperature, react 1～2h again; Adding 0.3～0.7mol divalent alcohol and material gross weight (is that the reaction raw materials diprotic acid is or/and the weight sum of dibasic acid anhydride, deionized water, NSC 7352, divalent alcohol, catalyzer, stopper; The back with) 0.07～0.30% the catalyzer and the stopper of material gross weight 0.03～0.07%, and progressively be warming up to 200 ℃～210 ℃ and carry out polycondensation 0.5～1h; Obtain polymkeric substance after the vacuum hydro-extraction; Adding vinylbenzene again dilutes and promptly makes product.
In the content of the present invention: described diprotic acid is a FUMARIC ACID TECH GRADE, and described dibasic acid anhydride is a MALEIC ANHYDRIDE; Said diprotic acid is or/and dibasic acid anhydride can be the mixtures that any or two kinds in the FUMARIC ACID TECH GRADE MALEIC ANHYDRIDE form with any proportioning.
In the content of the present invention: described divalent alcohol can be any or any two mixture that forms with any proportioning in terepthaloyl moietie, Ucar 35, glycol ether, the DPG.
In the content of the present invention: described catalyzer can be the mixtures that any or two kinds in sodium-acetate, X 2073, paratoluenesulfonic acid sodium salt, the Dibutyltin oxide form with any proportioning.
In the content of the present invention: described stopper can be Resorcinol, para benzoquinone, 2, any in the 6-di-tert-butyl methyl phenol or two kinds of mixtures that form with any proportioning.
In the content of the present invention: the time of said dropping NSC 7352 is 1～2h preferably.
In the content of the present invention: the time of said vacuum hydro-extraction is 1～2h preferably.
In the content of the present invention: said cinnamic add-on is preferably said polymer weight 42%～45%.
In the content of the present invention: said synthetic thickenable dicyclopentadiene unsaturated polyester resin is suitable for the matrix resin of making unsaturated polyester die plastic.
In the content of the present invention: said reactor drum is the reactor drum that is equipped with whisking appliance, TM, reflux exchanger, dropper.
Viscosity 932～the 1420mPas (25 ℃) of the thickenable dicyclopentadiene unsaturated polyester resin product of the present invention's preparation, acid number 17.9～24.8mgKOH/g.Resin thickening test (add white lake and the 1g activated magnesia of 150g particle diameter 15 μ m in the 100g resin, stir, and store 12h at 40 ℃) back resin paste viscosity increases to 9500～14700Pas (25 ℃).
Compared with prior art, the present invention has following characteristics and beneficial effect:
(1) the present invention adopts the multistep processes synthetic technology, processing ease, and the molecular resin amount is even, constant product quality, technology is simple, is easy to industry and enlarges production, and is practical;
(2) molecular resin amount of the present invention is higher, and acid number is stable, but the resin thickening has overcome the problem that original resin can not thickening, can be as the matrix resin of unsaturated polyester die plastic;
(3) the industrial by-products NSC 7352 of preparing method's employing of the present invention is made starting material, and price is lower, help reducing cost, but than similar thickening unsaturated polyester resin cost low about 20%.
Embodiment
Embodiment below the present invention is only as the further specifying of content of the present invention, can not be as scope perhaps in the qualification of the present invention.Below in conjunction with embodiment the present invention is made further detailed description.
Embodiment 1:
A kind of preparation method of thickenable dicyclopentadiene unsaturated polyester resin; Be in being equipped with the 1000mL four-hole boiling flask of whisking appliance, TM, reflux exchanger, tap funnel; Add 150g (1.530mol) MALEIC ANHYDRIDE, 27.5g (1.530mol) deionized water; Open to stir, be warming up to 100 ℃～140 ℃ insulation 1h reaction that is hydrolyzed; Drip 130g (0.902mol) NSC 7352, dropping time 1h in 110 ℃～180 ℃; Drip back anti-1h under this temperature; Add 45g (0.789mol) terepthaloyl moietie, catalyst acetic acid sodium 0.25g (0.00305mol), stopper para benzoquinone 0.12g (0.00111mol), and progressively be warming up to 200 ℃～210 ℃ polycondensations of dewatering; When the reactant acid number reaches 65mgKOH/g, vacuum hydro-extraction; When the reactant acid number reaches 30mgKOH/g～35mgKOH/g, remove vacuum and cooling; When temperature of charge was reduced to below 160 ℃, dilution promptly made product in the adding 135g vinylbenzene.Product viscosity 1180mPas (25 ℃), gel time 3.2min (126 ℃), acid number 21.3mgKOH/g.Resin thickening test (add white lake and the 1g activated magnesia of 150g particle diameter 15 μ m in the 100g resin, stir, and store 12h at 40 ℃, down together) back resin paste viscosity increases to 12400Pas (25 ℃).
Embodiment 2:
The NSC 7352 add-on is increased to 176g (1.224mol), and the terepthaloyl moietie add-on is reduced to 28g (0.459mol), and other is with embodiment 1 (summary).Product viscosity 1075mPas (25 ℃), gel time 2.8min (126 ℃), acid number 19.7mgKOH/g.Resin thickening test back resin paste viscosity increases to 9700Pas (25 ℃).
Embodiment 3:
The NSC 7352 add-on is reduced to 88g (0.612), and the terepthaloyl moietie add-on increases to 66g (1.071mol), and other is with embodiment 1 (summary).Product viscosity 1138mPas (25 ℃), gel time 3.4min (126 ℃), acid number 22.3mgKOH/g.Resin thickening test back resin paste viscosity increases to 11800Pas (25 ℃).
Embodiment 4:
The terepthaloyl moietie add-on is increased to 50g (0.805mol), and other is with embodiment 1 (summary).Product viscosity 986mPas (25 ℃), gel time 3.5min (126 ℃), acid number 18.2mgKOH/g.Resin thickening test back resin paste viscosity increases to 10500Pas (25 ℃).
Embodiment 5:
The deionized water add-on is increased to 33g (1.836mol), and other is with embodiment 1 (summary).Product viscosity 1150mPas (25 ℃), gel time 3.4min (126 ℃), acid number 21.8mgKOH/g.Resin thickening test back resin paste viscosity increases to 11500Pas (25 ℃).
Embodiment 6:
With catalyst change is X 2073, and add-on becomes 1.05g (0.00301mol), and other is with embodiment 1 (summary).Product viscosity 1265mPas (25 ℃), gel time 2.7min (126 ℃), acid number 20.7mgKOH/g.Resin thickening test back resin paste viscosity increases to 14700Pas (25 ℃).
Embodiment 7:
With catalyst change is paratoluenesulfonic acid sodium salt, and add-on becomes 0.60g (0.00309mol), and other is with embodiment 1 (summary).Product viscosity 1420mPas (25 ℃), gel time 2.5min (126 ℃), acid number 19.7mgKOH/g.Resin thickening test back resin paste viscosity increases to 9900Pas (25 ℃).
Embodiment 8:
With catalyst change is Dibutyltin oxide, and add-on becomes 0.75g (0.00301mol), and other is with embodiment 1 (summary).Product viscosity 1036mPas (25 ℃), gel time 3.3min (126 ℃), acid number 23.5mgKOH/g.Resin thickening test back resin paste viscosity increases to 13200Pas (25 ℃).
Embodiment 9:
Stopper is changed to Resorcinol, and add-on becomes 0.12g (0.00109mol), and other is with embodiment 1 (summary).Product viscosity 1280mPas (25 ℃), gel time 3.7min (126 ℃), acid number 22.5mgKOH/g.Resin thickening test back resin paste viscosity increases to 14300Pas (25 ℃).
Embodiment 10:
Stopper is changed to 2, the 6-di-tert-butyl methyl phenol, add-on becomes 0.25g (0.00109mol), and other is with embodiment 1 (summary).Product viscosity 1240m Pas (25 ℃), gel time 3.1min (126 ℃), acid number 21.7mgKOH/g.Resin thickening test back resin paste viscosity increases to 13200Pas (25 ℃).
Embodiment 11:
NSC 7352 is dripped time lengthening to 3h, drip the back this following reaction times of temperature to 2h, other is with embodiment 1 (summary).Product viscosity 1360m Pas (25 ℃), gel time 2.3min (126 ℃), acid number 17.9mgKOH/g.Resin thickening test back resin paste viscosity increases to 9500Pas (25 ℃).
Embodiment 12:
The NSC 7352 dropping time is foreshortened to 1h, drip the back and foreshorten to 1h in this following reaction times of temperature, other is with embodiment 1 (summary).Product viscosity 1170m Pas (25 ℃), gel time 3.3min (126 ℃), acid number 19.2mgKOH/g.Resin thickening test back resin paste viscosity increases to 11300Pas (25 ℃).
Embodiment 13:
The add-on of MALEIC ANHYDRIDE is reduced to 75g (0.765mol), add FUMARIC ACID TECH GRADE 88.8g (0.765mol), the add-on of softening water is reduced to 13.8g (0.765mol), other is with embodiment 1 (summary).Product viscosity 986m Pas (25 ℃), gel time 3.5min (126 ℃), acid number 18.2mgKOH/g.Resin thickening test back resin paste viscosity increases to 10300Pas (25 ℃).
Embodiment 14:
Terepthaloyl moietie is changed to Ucar 35, and add-on becomes 60g (0.789mol), and other is with embodiment 11 (summary).Products obtained therefrom viscosity 1325m Pas (25 ℃), gel time 3.0min (126 ℃), acid number 21.7mgKOH/g.Resin thickening test back resin paste viscosity increases to 13600Pas (25 ℃).
Embodiment 15:
Terepthaloyl moietie is changed to glycol ether, and add-on becomes 83.7g (0.789mol), and other is with embodiment 11 (summary).Products obtained therefrom viscosity 1030m Pas (25 ℃), gel time 3.2min (126 ℃), acid number 21.0mgKOH/g.Resin thickening test back resin paste viscosity increases to 11200Pas (25 ℃).
Embodiment 16:
Terepthaloyl moietie is changed to DPG, and add-on becomes 106g (0.790mol), and other is with embodiment 11 (summary).Products obtained therefrom viscosity 995m Pas (25 ℃), gel time 2.9min (126 ℃), acid number 21.1mgKOH/g.Resin thickening test back resin paste viscosity increases to 10200Pas (25 ℃).
Embodiment 17:
Terepthaloyl moietie is changed to Ucar 35, and add-on becomes 60g (0.789mol), and other is with embodiment 11 (summary).Products obtained therefrom viscosity 1325m Pas (25 ℃), gel time 3.0min (126 ℃), acid number 21.7mgKOH/g.Resin thickening test back resin paste viscosity increases to 12900Pas (25 ℃).
Embodiment 18:
The add-on of terepthaloyl moietie is reduced to 24.5g (0.395mol), add glycol ether 41.9g (0.395mol), other is with embodiment 11 (summary).Products obtained therefrom viscosity 1225m Pas (25 ℃), gel time 3.2min (126 ℃), acid number 20.7mgKOH/g.Resin thickening test back resin paste viscosity increases to 13900Pas (25 ℃).
Embodiment 19:
The add-on of catalyst acetic acid sodium is reduced to 0.20g (0.00244mol), and other is with embodiment 11 (summary).Products obtained therefrom viscosity 932m Pas (25 ℃), gel time 3.8min (126 ℃), acid number 24.8mgKOH/g.Resin thickening test back resin paste viscosity increases to 10400Pas (25 ℃).
Embodiment 20:
The NSC 7352 add-on is reduced to 120g (0.832), and the terepthaloyl moietie add-on increases to 50g (0.805mol), and other is with embodiment 11 (summary).Products obtained therefrom viscosity 1070m Pas (25 ℃), gel time 2.8min (126 ℃), acid number 20.4mgKOH/g.Resin thickening test back resin paste viscosity increases to 11600m Pas (25 ℃).
The invention is not restricted to the foregoing description, content of the present invention is said all can implement and have said good result.
Claims (10)
1. the preparation method of a thickenable dicyclopentadiene unsaturated polyester resin; It is characterized in that: in being equipped with the 1000mL four-hole boiling flask of whisking appliance, TM, reflux exchanger, tap funnel; Add 150g MALEIC ANHYDRIDE, 27.5g deionized water; Open to stir, be warming up to 100 ℃～140 ℃ insulation 1h reaction that is hydrolyzed; Drip the 130g NSC 7352, dropping time 1h in 110 ℃～180 ℃; Drip the back and under this temperature, react 1h; Add 45g terepthaloyl moietie, catalyst acetic acid sodium 0.25g, stopper para benzoquinone 0.12g, and progressively be warming up to 200 ℃～210 ℃ polycondensations of dewatering; When the reactant acid number reaches 65mgKOH/g, vacuum hydro-extraction; When the reactant acid number reaches 30mgKOH/g～35mgKOH/g, remove vacuum and cooling; When temperature of charge was reduced to below 160 ℃, dilution promptly made product in the adding 135g vinylbenzene.
2. by the preparation method of the said thickenable dicyclopentadiene unsaturated polyester resin of claim 1, it is characterized in that: said 130g NSC 7352 replaces with the 176g NSC 7352, and said 45g terepthaloyl moietie replaces with 28g terepthaloyl moietie.
3. by the preparation method of the said thickenable dicyclopentadiene unsaturated polyester resin of claim 1, it is characterized in that: said 45g terepthaloyl moietie replaces with 50g terepthaloyl moietie.
4. by the preparation method of the said thickenable dicyclopentadiene unsaturated polyester resin of claim 1, it is characterized in that: said 27.5g deionized water replaces with the 33g deionized water.
5. by the preparation method of the said thickenable dicyclopentadiene unsaturated polyester resin of claim 1, it is characterized in that: said catalyst acetic acid sodium 0.25g replaces with catalyzer Dibutyltin oxide 0.75g.
6. by the preparation method of the said thickenable dicyclopentadiene unsaturated polyester resin of claim 1, it is characterized in that: said dropping time 1h; Drip the back and under this temperature, react 1h; Replace with: drip time 3h; Drip the back and under this temperature, react 2h.
7. by the preparation method of the said thickenable dicyclopentadiene unsaturated polyester resin of claim 1, it is characterized in that: said 45g terepthaloyl moietie replaces with the 0g Ucar 35.
8. by the preparation method of the said thickenable dicyclopentadiene unsaturated polyester resin of claim 1, it is characterized in that: said 45g terepthaloyl moietie replaces with the 83.7g glycol ether.
9. by the preparation method of the said thickenable dicyclopentadiene unsaturated polyester resin of claim 1, it is characterized in that: said 45g terepthaloyl moietie replaces with 24.5g terepthaloyl moietie, adds glycol ether 41.9g.
10. by the preparation method of the said thickenable dicyclopentadiene unsaturated polyester resin of claim 1, it is characterized in that: said 130g NSC 7352 replaces with the 120g NSC 7352; Said 45g terepthaloyl moietie replaces with 50g terepthaloyl moietie.
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| CN101747608A (en) * | 2009-12-11 | 2010-06-23 | 上海新天和树脂有限公司 | Dicyclopentadiene-type unsaturated polyester mould pressing resin as well as preparation method and application thereof |
| CN104761711B (en) * | 2014-01-02 | 2017-01-18 | 上海龙怡机电材料有限公司 | Method used for modifying unsaturated polyester resin with dicyclopentadiene |
| CN109369897B (en) * | 2018-10-25 | 2020-05-08 | 江门市长河化工实业集团有限公司 | Soybean oil fatty acid modified dicyclopentadiene type unsaturated polyester resin |
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| US6384151B1 (en) * | 1999-02-05 | 2002-05-07 | Nippon Shokubai Co., Ltd. | Dicyclopentadiene-modified unsaturated polyester and process for producing the same as well as resin composition and molding material each containing unsaturated polyester |
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| US6384151B1 (en) * | 1999-02-05 | 2002-05-07 | Nippon Shokubai Co., Ltd. | Dicyclopentadiene-modified unsaturated polyester and process for producing the same as well as resin composition and molding material each containing unsaturated polyester |
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