CN116120535A - Modified unsaturated polyester and preparation method thereof - Google Patents
Modified unsaturated polyester and preparation method thereof Download PDFInfo
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- CN116120535A CN116120535A CN202310401881.7A CN202310401881A CN116120535A CN 116120535 A CN116120535 A CN 116120535A CN 202310401881 A CN202310401881 A CN 202310401881A CN 116120535 A CN116120535 A CN 116120535A
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- unsaturated polyester
- dicyclopentadiene
- polymerization inhibitor
- pet
- modified unsaturated
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- 229920006305 unsaturated polyester Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 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 claims abstract description 33
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 239000003112 inhibitor Substances 0.000 claims abstract description 28
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 6
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 6
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 15
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical group CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 229920005989 resin Polymers 0.000 abstract description 15
- 239000011347 resin Substances 0.000 abstract description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 229920000728 polyester Polymers 0.000 abstract description 11
- 229920006337 unsaturated polyester resin Polymers 0.000 abstract description 9
- 230000032683 aging Effects 0.000 abstract description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 15
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 12
- 238000006136 alcoholysis reaction Methods 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- -1 dicyclopentadiene maleic acid diester Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Relates to the technical field of unsaturated polyester resin, in particular to modified unsaturated polyester and a preparation method thereof. Terephthalic acid needs strong acid as a catalyst at high temperature to react with dihydric alcohol to prepare polyester, and the generated polyester has poor compatibility with styrene and is easy to laminate, so that the production and application of the terephthalic type unsaturated resin are greatly limited. The invention comprises the following raw materials in percentage by weight: PET, diethylene glycol, benzoic acid, phthalic anhydride, ethylene glycol, maleic anhydride, dicyclopentadiene, a catalyst, an antioxidant and a polymerization inhibitor, and the balance of water; the mol number of dicyclopentadiene accounts for 14.5-33% of the total mol number of alcohol in the raw material; the mole number of PET accounts for 34-35% of the total mole number of alcohol in the raw material. The reaction difficulty is reduced by utilizing PET and dicyclopentadiene, the problem of poor compatibility of the para-benzene type unsaturated polyester and styrene is solved, and the problem that the pure dicyclopentadiene modified resin is not ageing-resistant is solved.
Description
Technical Field
Relates to the technical field of unsaturated polyester resin, in particular to modified unsaturated polyester and a preparation method thereof.
Background
The two carboxyl groups of terephthalic acid are positioned at para positions of benzene rings, so that the interaction is small, and the chemical property is stable; the unsaturated resin produced by the reaction of terephthalic acid has good molecular symmetry and neat structure, and shows good mechanical property and excellent corrosion resistance and heat resistance. But the reaction activity is low, the reaction condition is high, strong acid is needed as a catalyst at high temperature to react with dihydric alcohol, the generated polyester has poor compatibility with styrene, layering is easy, and the production and application of the p-benzene type unsaturated resin are greatly limited.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: overcomes the defects of the prior art, and provides a modified unsaturated resin with good compatibility with styrene, aging resistance, low reaction difficulty and small environmental load and a preparation method thereof.
The technical scheme adopted for solving the technical problems is as follows: a modified unsaturated polyester characterized in that: the raw materials comprise the following components in percentage by weight: 25-31% of PET, 23-29% of diethylene glycol, 2-4% of benzoic acid, 3-8% of phthalic anhydride, 1-3% of ethylene glycol, 20-25% of maleic anhydride, 9-16% of dicyclopentadiene, 0.05-0.06% of a catalyst, 0.05-0.07% of an antioxidant, 0.001-0.002% of a polymerization inhibitor and the balance of water; wherein the mol number of dicyclopentadiene accounts for 14.5-33% of the total mol number of alcohol in the raw material; the mole number of PET accounts for 34-35% of the total mole number of alcohol in the raw material.
The two carboxyl groups of terephthalic acid are at the para position of benzene ring, the molecular structure is symmetrical, the dipole moment is equal to zero, the polyester produced by using the terephthalic acid has large crystallization tendency, poor compatibility with styrene, easy layering and influence on use. The dicyclopentadiene is adopted for addition, so that on one hand, the symmetry of the molecular structure of the polyester is destroyed, and the crystallization capability of the polyester is reduced; on the other hand, according to the similar compatibility principle, the dicyclopentadiene has a structure similar to that of styrene, and both aspects are beneficial to the compatibility of the para-benzene type polyester and the styrene. The mol number of dicyclopentadiene is lower than 14.5%, the compatibility of unsaturated polyester and styrene is poor, and the effect of dicyclopentadiene in the reaction system is not reflected; if the content is higher than 33%, the excessive dicyclopentadiene is decomposed into cyclopentadiene in the later temperature rising process, and the cyclopentadiene and unsaturated double chains in a polyester molecular chain undergo an addition reaction, so that the unsaturated double bonds of the polyester are reduced, the activity is reduced, the curing speed is reduced, the resin gelation time is too long, and the resin is not beneficial to use. The proportion of dicyclopentadiene to PET is in the corresponding range, and unsaturated polyester molecules generated by the reaction do not play a role due to too little dicyclopentadiene section, and the original excellent performance of the parabenzene resin is not lost due to too much dilution of the parabenzene section.
Preferably, the mol number of dicyclopentadiene accounts for 29-54% of the total mol number of maleic anhydride in the raw material.
The reaction increases the proportion of cis-butadiene anhydride, which is favorable for the progress of the synthesis reaction and improves the yield and purity of the product, but the excessive proportion of cis-butadiene anhydride generates a byproduct dicyclopentadiene maleic acid diester; the proportion is too low, and dicyclopentadiene is decomposed into cyclopentadiene as a byproduct. Both byproducts darken the final product and affect the color of the final product unsaturated resin. With a molar ratio in this range, the two by-products are less and the strength of the final unsaturated polyester cured product is excellent.
Preferably, the catalyst is dibutyl tin oxide and zinc acetate in a weight ratio of 1: 4.
Among a plurality of metal ions, zinc ions have the best catalytic effect, zinc acetate is used as a metal salt, has high catalytic activity, can be dissolved in a solvent at a higher temperature and fully contacts with reactants, and accelerates the alcoholysis reaction process; the dibutyl tin oxide is used as a composite metal oxide, has more acid sites and interaction between zinc and tin ions compared with other single metal oxides, and has better catalytic effect. However, zinc acetate is corrosive as Lewis acid, and the proportion of the compound catalyst is selected to reduce the corrosion to the reaction kettle and reduce the production cost on the premise of ensuring the catalytic effect.
Preferably, the polymerization inhibitor is hydroquinone and ketone naphthenate according to the weight ratio of 2: 1.
Hydroquinone is added in alcoholysis and polycondensation reaction, so that the early reaction speed is slowed down, the occurrence of polymerization explosion in the polycondensation reaction is prevented, and a single polymerization inhibitor is selected for the first polymerization inhibition, thereby being convenient for adjusting the gelation time of a final product in actual production; the cycloalkanone is selected so as to ensure the storage stability of the product in the latter stage.
Preferably, the antioxidant is a mixture of 2, 6-p-tert-butylxylenol and triphenyl phosphite in a weight ratio of 1:1.
Preferably, the moles of PET account for 60% of the total moles of diethylene glycol in the feed.
When the diethylene glycol consumption is low, the alcoholysis efficiency is low, and as the diethylene glycol consumption is increased, more diethylene glycol molecules penetrate into the PET material, so that more PET molecules swell and decompose, and the corresponding alcoholysis degree is increased. However, the alcoholysis efficiency of PET is reduced along with the increase of the consumption of diethylene glycol, and the reason is that the effect of swelling PET is limited after the consumption of diethylene glycol is excessive, so that the degradation of PET is not greatly influenced, and the relative concentration of PET is reduced due to the use of excessive diethylene glycol. Therefore, the ratio is most suitable for considering the reduction of raw materials and the alcoholysis efficiency.
The preparation method of the modified unsaturated polyester is characterized by comprising the following steps: the method comprises the following steps:
1) Mixing PET, diethylene glycol, benzoic acid, phthalic anhydride, ethylene glycol, a catalyst and an antioxidant, heating to 200-220 ℃, and stirring until the acid value is lower than 5mgKOH/g;
2) Mixing water, dicyclopentadiene and an antioxidant, heating to 120 ℃, dropwise adding maleic anhydride, heating to 125-130 ℃, and preserving heat for 2-3 hours;
3) Mixing the mixture obtained in the step 1) and the step 2), adding a polymerization inhibitor, heating to 150-170 ℃ and preserving heat for 0.5-1.5 h; continuously heating to 200-220 ℃, and preserving heat until the acid value is 14-20 mgKOH/g;
4) Cooling to 120-180 ℃, and adding a polymerization inhibitor and styrene to obtain modified unsaturated polyester;
wherein, the antioxidant in the step 1) is 50-70% of the total amount of the antioxidants in the raw materials, and the antioxidant in the step 2) is the rest of the antioxidants in the raw materials; the polymerization inhibitor in the step 3) is 20-30% of the total amount of the polymerization inhibitor in the raw materials, and the polymerization inhibitor in the step 4) is the total amount of the polymerization inhibitor in the raw materials.
Preferably, the cooling in step 4) is as follows: firstly cooling to 180 ℃ or lower, adding a polymerization inhibitor, then cooling to 120-130 ℃ and adding styrene.
Compared with the prior art, the invention has the following beneficial effects: 1. the addition of PET modification to replace terephthalic acid reduces the reaction difficulty, avoids the introduction of a concentrated sulfuric acid catalyst required by terephthalic acid reaction, and has the advantages of low environmental burden due to the PET recycling material. 2. The problem of poor compatibility of the p-benzene type unsaturated polyester and styrene is solved by modifying dicyclopentadiene, the physical property of the resin is further improved, and excessive dicyclo can lead to lower system viscosity, prolonged gelation time and possibly lower strength of the unsaturated polyester. 3. The problem that the pure dicyclopentadiene modified resin is not ageing-resistant is solved by modifying the PET with the para-benzene.
Detailed Description
The present invention will be further described with reference to the following examples, with example 1 being the best mode of carrying out the invention.
A preparation method of modified unsaturated polyester comprises the following steps:
1) Mixing PET, diethylene glycol, benzoic acid, phthalic anhydride, ethylene glycol, a catalyst and an antioxidant, heating to 200-220 ℃, and stirring until the acid value is lower than 5mgKOH/g;
2) Mixing water, dicyclopentadiene and an antioxidant, heating to 120 ℃, starting to dropwise add maleic anhydride for 2 hours, heating to 125-130 ℃, preserving heat for 2.5 hours, and cooling;
3) Adding a polymerization inhibitor, heating to 150-170 ℃ and preserving heat for 1h; continuously heating, controlling the temperature to be 200-220 ℃ and preserving the temperature until the acid value is 14-20 mgKOH/g (sampling monitoring is started after the temperature reaches 0.5 h);
4) Cooling to 180 ℃, adding a polymerization inhibitor, continuously cooling to 130 ℃, adding styrene (the temperature of the added process is 120-130 ℃, and the mixing of styrene is prevented from being influenced by the low temperature), so as to obtain modified unsaturated polyester;
wherein, the antioxidant in the step 1) is 50-70% of the total amount of the antioxidants in the raw materials, and the antioxidant in the step 2) is the rest of the antioxidants in the raw materials; the polymerization inhibitor in the step 3) is 25% of the total amount of the polymerization inhibitor in the raw materials, and the polymerization inhibitor in the step 3) is the total amount of the polymerization inhibitor in the raw materials.
Examples 1 to 8
The proportions of the raw materials of examples 1 to 8 are shown in Table 1 below, and the unit of the amount of each raw material in Table 1 is g.
Table 1 example raw materials table
The catalyst is dibutyl tin oxide and zinc acetate according to the weight ratio of 1: 4; the antioxidant is 2, 6-p-tert-butyl xylenol; the polymerization inhibitor is hydroquinone and copper naphthenate according to the weight ratio of 2:1, wherein the polymerization inhibitor in the step 3) is 50% of the total amount of hydroquinone, and the polymerization inhibitor in the step 4) is the total amount of hydroquinone and total ketone naphthenate.
Comparative examples 1 to 5
The raw material ratios of the modified unsaturated polyesters of comparative examples 1 to 5 are shown in Table 2 below.
Table 2 comparative example raw material table
Wherein, PET was not added in comparative example 1; a small amount of dicyclopentadiene out of range was added to comparative example 2; in comparative example 3, an excess of dicyclopentadiene was added; in comparative example 4, dicyclopentadiene was not added; a small amount of dicyclopentadiene was added in comparative example 5.
Performance testing
1. Appearance of
And standing the prepared unsaturated polyester resin, observing whether the unsaturated polyester resin is layered or not, storing the unsaturated polyester resin at a low temperature, and observing whether the unsaturated polyester resin is layered or not.
2. Aging resistance
And (3) preparing the prepared unsaturated polyester resin into a color plate required by an aging test, putting the color plate into an ultraviolet accelerated weathering test machine, and carrying out a comparative aging test, wherein the test result is taken as a comparison of 200 h. The delta E represents the change amount, and the smaller the change amount is, the stronger the aging resistance is.
3. Gel time
The obtained unsaturated polyester resin was subjected to gel time measurement at 25℃according to the requirements of standard GB 7193-2008.
4. Flexural Strength
The resulting unsaturated polyester resin was tested for flexural strength as required by standard GB/T2567-2021.
The test results of examples and comparative examples are shown in Table 3 below:
TABLE 3 Performance test results
In comparative example 1, no p-benzene molecular segment is added, and compared with the examples, the ageing resistance and bending strength are poor; comparative example 2 beyond the range of the examples, too much dicyclopentadiene was decomposed into cyclopentadiene as a byproduct during the reaction, resulting in darkening of the resin; the excessive cyclopentadiene is used as a monofunctional small molecule to be added with unsaturated double bonds, so that the resin gel time is prolonged; comparative example 3 the molar ratio of dicyclopentadiene to maleic anhydride was largely outside the range of the examples, a large amount of excess dicyclopentadiene decomposed a large amount of cyclopentadiene by-products during the reaction, reacted with unsaturated double bonds during the curing process and consumed a large amount of initiator radicals, so that the resin had no gelation tendency, the cured product had insufficient curing degree, and the bending property was greatly reduced; in comparative example 4, dicyclopentadiene was not added, but as a pure para-benzene resin, the compatibility with styrene was poor, and the disadvantage of delamination by standing was revealed; comparative example 5 the addition of dicyclopentadiene below the range of examples, at first, the low addition of dicyclopentadiene does not effectively destroy the structural symmetry and crystallization ability of the p-phenylene polyester molecule, the compatibility of the polyester with styrene is not effectively improved, the phenomenon of poor compatibility still occurs at low temperature, and the bending strength is also greatly different from that of examples.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (7)
1. A modified unsaturated polyester characterized in that: the raw materials comprise the following components in percentage by weight: 25-31% of PET, 23-29% of diethylene glycol, 2-4% of benzoic acid, 3-8% of phthalic anhydride, 1-3% of ethylene glycol, 20-25% of maleic anhydride, 9-16% of dicyclopentadiene, 0.05-0.06% of a catalyst, 0.05-0.07% of an antioxidant, 0.001-0.002% of a polymerization inhibitor and the balance of water; wherein the mol number of dicyclopentadiene accounts for 14.5-33% of the total mol number of alcohol in the raw material; the mole number of PET accounts for 34-35% of the total mole number of alcohol in the raw material.
2. The modified unsaturated polyester of claim 1, characterized in that: the mole number of dicyclopentadiene accounts for 29-54% of the total mole number of maleic anhydride in the raw material.
3. The modified unsaturated polyester of claim 1, characterized in that: the catalyst is dibutyl tin oxide and zinc acetate according to the weight ratio of 1: 4.
4. The modified unsaturated polyester of claim 1, characterized in that: the polymerization inhibitor is prepared from hydroquinone and ketone naphthenate according to a weight ratio of 2: 1.
5. The modified unsaturated polyester of claim 1, characterized in that: the antioxidant is a mixture of 2, 6-p-tert-butylxylenol and triphenyl phosphite according to a weight ratio of 1:1.
6. The modified unsaturated polyester of claim 1, characterized in that: the mole number of the PET accounts for 60% of the total mole number of the diethylene glycol in the raw material.
7. A process for producing the modified unsaturated polyester according to any one of claims 1 to 6, characterized in that: the method comprises the following steps:
1) Mixing PET, diethylene glycol, benzoic acid, phthalic anhydride, ethylene glycol, a catalyst and an antioxidant, heating to 200-220 ℃, and stirring until the acid value is lower than 5mgKOH/g;
2) Mixing water, dicyclopentadiene and an antioxidant, heating to 120 ℃, dropwise adding maleic anhydride, heating to 125-130 ℃, and preserving heat for 2-3 hours;
3) Mixing the mixture obtained in the step 1) and the step 2), adding a polymerization inhibitor, heating to 150-170 ℃ and preserving heat for 0.5-1.5 h; continuously heating to 200-220 ℃, and preserving heat until the acid value is 14-20 mgKOH/g;
4) Cooling to 120-180 ℃, and adding a polymerization inhibitor and styrene to obtain modified unsaturated polyester;
wherein, the antioxidant in the step 1) is 50-70% of the total amount of the antioxidants in the raw materials, and the antioxidant in the step 2) is the rest of the antioxidants in the raw materials; the polymerization inhibitor in the step 3) is 20-30% of the total amount of the polymerization inhibitor in the raw materials, and the polymerization inhibitor in the step 4) is the total amount of the polymerization inhibitor in the raw materials.
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Denomination of invention: A modified unsaturated polyester and its preparation method Effective date of registration: 20231026 Granted publication date: 20230620 Pledgee: Industrial and Commercial Bank of China Limited Jingmen Duodao Branch Pledgor: Hubei Wanglin New Material Technology Co.,Ltd. Registration number: Y2023980062557 |