CN115449064B - Artificial quartz stone unsaturated polyester resin and preparation method thereof - Google Patents
Artificial quartz stone unsaturated polyester resin and preparation method thereof Download PDFInfo
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- CN115449064B CN115449064B CN202211402468.4A CN202211402468A CN115449064B CN 115449064 B CN115449064 B CN 115449064B CN 202211402468 A CN202211402468 A CN 202211402468A CN 115449064 B CN115449064 B CN 115449064B
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- terephthalic acid
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- 229920006337 unsaturated polyester resin Polymers 0.000 title claims abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000010453 quartz Substances 0.000 title claims abstract description 32
- 239000004575 stone Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 50
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 42
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 40
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 30
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920002215 polytrimethylene terephthalate Polymers 0.000 claims abstract description 25
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 17
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 16
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 13
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- 239000003112 inhibitor Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- -1 polytrimethylene terephthalate Polymers 0.000 claims abstract description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical group CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 8
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 8
- 239000012188 paraffin wax Substances 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 4
- 238000012544 monitoring process Methods 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims 2
- 229920000728 polyester Polymers 0.000 abstract description 24
- 229920006305 unsaturated polyester Polymers 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011230 binding agent Substances 0.000 abstract description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 20
- GINJFDRNADDBIN-FXQIFTODSA-N bilanafos Chemical compound OC(=O)[C@H](C)NC(=O)[C@H](C)NC(=O)[C@@H](N)CCP(C)(O)=O GINJFDRNADDBIN-FXQIFTODSA-N 0.000 description 12
- 238000011056 performance test Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229920001225 polyester resin Polymers 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010125 resin casting Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 239000004135 Bone phosphate Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000011044 quartzite Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- 238000009827 uniform distribution Methods 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)
Abstract
An artificial quartz unsaturated polyester resin and a preparation method thereof, belonging to the technical field of artificial quartz unsaturated polyester. The quartz stone plate produced by using the existing unsaturated polyester resin as a binder has poor temperature resistance and is easy to deform at high temperature, so that the application of the existing unsaturated polyester resin for artificial quartz stone is limited. The raw materials of the invention comprise terephthalic acid, maleic anhydride, phthalic anhydride, propylene glycol, ethylene glycol, diethylene glycol, polytrimethylene terephthalate (PTT), benzoic acid, styrene, polymerization inhibitor, catalyst and antioxidant. The mechanical property, the heat deformation resistance and the water and stain resistance of the prepared polyester are obviously improved by utilizing the terephthalic acid, the phthalic anhydride, the propanediol and the PTT.
Description
Technical Field
An artificial quartz unsaturated polyester resin and a preparation method thereof, belonging to the technical field of artificial quartz unsaturated polyester.
Background
The artificial quartz stone is a building decoration material produced by using unsaturated polyester resin as a binder, adding inorganic fillers such as quartz sand, glass and the like, adding color paste and a curing agent, and carrying out molding processes such as mixing, distributing, vibrating and compressing, high-temperature curing and the like. The weight of the unsaturated polyester resin in the artificial quartz stone plate is approximately 8-15%, and the mechanical property and the heat distortion temperature of a resin casting body have direct influence on the quality and the comprehensive performance of the artificial quartz stone plate.
The unsaturated polyester resin for producing artificial quartz stone in the market is generally in a phthalic acid formula, raw materials of the unsaturated polyester resin mainly comprise ethylene glycol, diethylene glycol, propylene glycol, phthalic anhydride, maleic acid and styrene, the production process is generally divided into two steps, the first step is to perform polycondensation reaction on dibasic acid and dihydric alcohol to form unsaturated polyester, and the second step is to dissolve the polyester in the styrene to obtain the unsaturated polyester resin. The heat distortion temperature is low, and the material is easy to deform at high temperature, generally 45 to 55 ℃. The water resistance and stain resistance of the board are poor, and the comprehensive performance of the artificial quartz stone board is influenced.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art, provides the artificial quartz unsaturated polyester resin and the preparation method thereof, and has excellent mechanical property and heat deformation resistance.
The technical scheme adopted by the invention for solving the technical problems is as follows: an artificial quartz unsaturated polyester resin is characterized in that: the raw materials comprise, by weight, 150 to 300 parts of terephthalic acid, 400 to 500 parts of maleic anhydride, 20 to 100 parts of phthalic anhydride, 50 to 100 parts of propylene glycol, 20 to 100 parts of ethylene glycol, 550 to 650 parts of diethylene glycol, 300 to 450 parts of polytrimethylene terephthalate (PTT bottle flakes), 10 to 40 parts of benzoic acid, 740 to 760 parts of styrene, 0.3 to 0.7 part of polymerization inhibitor, 0.1 to 0.5 part of catalyst and 0.5 to 2 parts of antioxidant; carrying out condensation polymerization reaction on the raw materials to obtain artificial quartz unsaturated polyester resin;
the weight ratio of terephthalic acid in the raw materials is 5.3 to 12.5 percent; the weight ratio of the polytrimethylene terephthalate is 11.6 to 15.8 percent.
The polyester resin generated by terephthalic acid and unsaturated alcohol theoretically has better mechanical property and heat deformation resistance, but because the crystallinity of polyester formed by terephthalic acid is strong and the compatibility with styrene is poor, the unsaturated polyester is very easy to be turbid and layered when being prepared, and the unsaturated polyester cannot have good crosslinking effect with styrene, so the terephthalic acid is not adopted in the field of artificial quartz unsaturated polyester resin generally.
In the acid component, phthalic anhydride and benzoic acid are adopted, the phthalic anhydride can improve the compatibility of styrene, the benzoic acid is used for blocking a polyester chain, the polarity of a polyester group is changed, the lipophilicity of the polyester chain is enhanced, the compatibility of the polyester and the styrene can also be improved, a PTT polyester long chain is added, the PTT polyester long chain can be alcoholyzed into small molecules in a catalyst environment and grafted to the polyester long chain, the excellent mechanical property of the PTT can be provided, the problem of poor compatibility with the styrene caused by the introduction of terephthalic acid into the polyester resin can be further solved, and the turbid layering phenomenon of the unsaturated polyester resin is avoided; in the alcohol raw materials, the propylene glycol with the dosage can improve the compatibility of a polyester chain and styrene, improve the wetting dispersibility of the resin to a filler, is more suitable for the combination of inorganic fillers, and can also improve the stain resistance of an artificial quartz stone product, and the finally prepared polyester resin overcomes the problem of poor compatibility of terephthalic acid, so that the mechanical property, the heat deformation resistance and the water and stain resistance of the terephthalic acid to polyester are improved.
Preferably, the weight ratio of the terephthalic acid in the raw materials is 9.7%, and the weight ratio of the polytrimethylene terephthalate in the raw materials is 11.6%.
Under the preferable proportional relation, the compatibility improvement capability of the PTT to the polyester can be ensured, and the turbid layering phenomenon is avoided.
Preferably, the catalyst is zinc acetate.
The zinc acetate has little influence on the color of the polyester synthesis and is not easy to yellow, so that the finally prepared unsaturated polyester resin has good transparency and more uniform molecular chain distribution.
Preferably, the antioxidant is triphenyl phosphite.
Preferably, the polymerization inhibitor is methyl hydroquinone.
Preferably, the paint also comprises 0.05 to 0.2 part of paraffin.
The preparation method of the artificial quartz unsaturated polyester resin is characterized by comprising the following steps: the method comprises the following steps:
1) Mixing diethylene glycol, a catalyst, two fifths to one half of antioxidant, terephthalic acid and polytrimethylene terephthalate, heating to 180 to 190 ℃, keeping the temperature for 0.2 to 0.8h, heating to 210 to 220 ℃, and keeping the temperature until the acid value of the material is less than 5 mgKOH/g;
2) Cooling the material to be below 150 ℃, adding ethylene glycol, propylene glycol, two-fifths to one-half of polymerization inhibitor, residual antioxidant, maleic anhydride, phthalic anhydride and benzoic acid, heating to 205-210 ℃, carrying out heat preservation reaction, monitoring the acid value to be reduced to 50-60mgKOH/g, starting vacuumizing, monitoring the acid value to be reduced to 15-25mgKOH/g, and stopping heating;
3) Cooling to 180 ℃ or below, adding the residual polymerization inhibitor and paraffin, stirring uniformly, cooling to 120 ℃ or below, adding styrene, and stirring uniformly to obtain the artificial quartz stone unsaturated polyester resin.
The first step is to carry out alcoholysis of saturated dibasic acid and PTT to form micromolecule, and the second step is to add polymerization reaction of maleic anhydride (unsaturated dibasic acid). When the dihydric alcohol reacts with the dibasic acid, the maleic anhydride reacts preferentially with the dihydric alcohol due to its relatively high reactivity, and the molecular chain distribution is not uniform, thereby affecting the mechanical properties and the curing ability.
The preparation method is beneficial to ensuring the molecular weight of a polyester molecular chain, avoiding the reduction of the molecular weight due to early acid-alcohol reaction, and simultaneously being beneficial to the uniform distribution of saturated acid and unsaturated acid.
Compared with the prior art, the invention has the beneficial effects that: in the acid component, phthalic anhydride and benzoic acid are adopted, the phthalic anhydride can improve the compatibility of styrene, the benzoic acid is used for blocking a polyester chain, the polarity of the polyester group is changed, the lipophilicity of the polyester chain is enhanced, and the compatibility of the polyester and the styrene can also be improved, and a PTT polyester long chain is selected to be added, can be subjected to alcoholysis to form a small molecule in a catalyst environment, and can provide the excellent mechanical property of PTT after being grafted to the polyester long chain, the problem of poor compatibility with the styrene caused by the introduction of terephthalic acid into the polyester resin can be further solved, and the turbid layering phenomenon of the unsaturated polyester resin is avoided; in the alcohol raw materials, the propylene glycol with the dosage can improve the compatibility of a polyester chain and styrene, improve the wetting dispersibility of the resin to a filler, is more suitable for the combination of inorganic fillers, and can also improve the stain resistance of an artificial quartz stone product, and the finally prepared polyester resin overcomes the problem of poor compatibility of terephthalic acid, so that the mechanical property, the heat deformation resistance and the water-resistant stain resistance of the terephthalic acid to polyester are improved.
Detailed Description
The present invention is further illustrated by the following examples, example 3 being the best mode of carrying out the invention.
In the following examples and comparative examples, the following preparation method was used for the synthetic quartz unsaturated polyester resin:
1) Under the protection of nitrogen, putting diethylene glycol, a catalyst zinc acetate, one half of antioxidant triphenyl phosphite, terephthalic acid and PTT bottle flakes into a reaction kettle, starting stirring, heating to 185 ℃ under the protection of nitrogen, keeping the temperature for 0.5 hour, then heating and keeping the temperature at 210 to 220 ℃, and reacting until the acid value of a detected material is less than 5mgKOH/g, wherein the material is clear and transparent;
2) Cooling the obtained material to 150 ℃, adding ethylene glycol, propylene glycol, one-half weight of polymerization inhibitor methyl hydroquinone, the rest antioxidant triphenyl phosphite, maleic anhydride, phthalic anhydride and benzoic acid into a reaction kettle, raising the temperature at a constant speed after the feeding is finished, keeping the temperature at 205 to 210 ℃, reducing the pressure and vacuumizing when the acid value of the material is reduced to 50 to 60mgKOH/g, stopping heating when the acid value is detected to be reduced to 15 to 25mgKOH/g, and starting cooling equipment to reduce the temperature;
3) Adding the residual polymerization inhibitor and paraffin when the temperature of the reaction kettle material is reduced to 180 ℃, uniformly stirring, pressing the material to a dilution kettle, and adding styrene once for dilution when the temperature is reduced to 120 ℃; and stirring uniformly to obtain the unsaturated polyester resin.
Examples
The raw material composition of the artificial quartz unsaturated polyester resin of each example is shown in the following table 1.
Table 1 examples raw material table
Comparative example
The raw materials of the artificial quartz unsaturated polyester resin with various proportions are shown in the following table 2. Wherein, comparative example 1 is the case of adding no propylene glycol on the basis of example 1, and comparative example 2 is the case of excessively low contents of terephthalic acid and polytrimethylene terephthalate; comparative example 3 is the case of a conventional ortho-benzene type unsaturated polyester resin; comparative example 4~6 is the absence of phthalic anhydride, the absence of benzoic acid and the presence of too low of poly (trimethylene terephthalate), respectively.
Table 2 comparative examples raw material table
The preparation method of comparative example 3 adopts the following processes:
1) Adding the prepared diethylene glycol, ethylene glycol, propylene glycol, maleic anhydride, phthalic anhydride and tribasic phosphite (antioxidant) into a reaction kettle, starting stirring, heating under the protection of nitrogen, keeping the temperature at 205-210 ℃, reducing pressure and vacuumizing when the acid value of the material is reduced to 58mgKOH/g, stopping heating when the acid value of the material is reduced to 23mgKOH/g, and starting cooling equipment to reduce the temperature.
2) Adding methyl hydroquinone (polymerization inhibitor) and paraffin when the temperature of the materials in the reaction kettle is reduced to 180 ℃, uniformly stirring, pressing the materials to a dilution kettle, and adding styrene once for dilution when the temperature is reduced to 120 ℃; and sampling and detecting indexes after stirring uniformly, and obtaining the unsaturated polyester resin after the indexes are qualified.
In addition, in the preparation process of the comparative examples 2 and 6, serious resin turbidity delamination phenomenon occurs, and the finally obtained resin has poor light transmission effect.
Performance testing
The unsaturated polyester resin of artificial quartzite prepared in the above examples and comparative examples were subjected to the performance test, and the results of the performance test of the examples are shown in Table 3 below.
Table 3 results of performance testing of examples
Comparative examples the results of the performance tests are given in table 4 below.
Table 4 comparative example performance test results
And (3) comparing and analyzing performance test results:
(1) as described above, comparative example 4 and comparative example 5 exhibited severe resin haze delamination during the preparation process. The comparison with the examples shows that the polyester synthesized by adopting benzoic acid and phthalic anhydride has good compatibility with styrene, and the obtained unsaturated polyester resin has better transparency.
(2) Comparative example 3 compared to example 3, without the use of terephthalic acid and PTT bottle chips, the heat distortion temperature and mechanical properties were significantly lower than for the examples.
(3) Comparative example 1 used 120 parts by weight of ethylene glycol, and example 1 used 40 parts by weight of ethylene glycol and 90 parts by weight of propylene glycol, and it is seen from the performance test data that the tensile properties and bending properties of the resin-molded body were remarkably improved by using a specific amount of propylene glycol.
(4) Comparison of comparative example 2 with comparative example 3, example 2 found that the use of terephthalic acid and PTT bottle chips in place of a portion of phthalic acid significantly increases the heat distortion temperature of the resin-cast body, i.e., increases the heat resistance of the unsaturated polyester resin article.
(5) Compared with the comparative example 5, the 1,2,3,6 has the advantages that the mechanical property of the resin casting body is seriously influenced after the resin is layered and turbid, and the performance test data is greatly reduced.
According to the performance test results of the above examples and comparative examples, terephthalic acid can indeed play a good role in modifying the mechanical properties and heat resistance of the synthetic quartz unsaturated polyester resin, while the use of a proper amount of PTT, phthalic anhydride, benzoic acid and propylene glycol can effectively avoid the problem of turbid delamination caused by the introduction of terephthalic acid.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (5)
1. An artificial quartz unsaturated polyester resin is characterized in that: the raw materials comprise, by weight, 150 to 300 parts of terephthalic acid, 400 to 500 parts of maleic anhydride, 20 to 100 parts of phthalic anhydride, 50 to 100 parts of propylene glycol, 20 to 100 parts of ethylene glycol, 550 to 650 parts of diethylene glycol, 300 to 450 parts of polytrimethylene terephthalate, 10 to 40 parts of benzoic acid, 740 to 760 parts of styrene, 0.3 to 0.7 part of polymerization inhibitor, 0.05 to 0.2 part of paraffin, 0.1 to 0.5 part of catalyst and 0.5 to 2 parts of antioxidant; the raw materials are subjected to condensation reaction to prepare the artificial quartz unsaturated polyester resin;
in the raw materials, the weight ratio of terephthalic acid is 5.3 to 12.5 percent; the weight ratio of the polytrimethylene terephthalate is 11.6 to 15.8 percent;
the condensation reaction comprises the following steps:
1) Mixing diethylene glycol, a catalyst, two fifths to one half of antioxidant, terephthalic acid and polytrimethylene terephthalate, heating to 180 to 190 ℃, keeping the temperature for 0.2 to 0.8h, heating to 210 to 220 ℃, and keeping the temperature until the acid value of the material is less than 5 mgKOH/g;
2) Cooling the material to be below 150 ℃, adding ethylene glycol, propylene glycol, two-fifths to one-half of polymerization inhibitor, residual antioxidant, maleic anhydride, phthalic anhydride and benzoic acid, heating to 205-210 ℃, carrying out heat preservation reaction, monitoring the acid value to be reduced to 50-60mgKOH/g, starting vacuumizing, monitoring the acid value to be reduced to 15-25mgKOH/g, and stopping heating;
3) Cooling to 180 ℃ or below, adding the residual polymerization inhibitor and paraffin, stirring uniformly, cooling to 120 ℃ or below, adding styrene, and stirring uniformly to obtain the artificial quartz stone unsaturated polyester resin.
2. The artificial quartz unsaturated polyester resin according to claim 1, characterized in that: the weight ratio of terephthalic acid in the raw materials is 9.7%, and the weight ratio of polytrimethylene terephthalate is 11.6%.
3. The artificial quartz unsaturated polyester resin according to claim 1, characterized in that: the catalyst is zinc acetate.
4. The artificial quartz unsaturated polyester resin according to claim 1, characterized in that: the antioxidant is triphenyl phosphite.
5. The artificial quartz unsaturated polyester resin according to claim 1, characterized in that: the polymerization inhibitor is methyl hydroquinone.
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| CN202211402468.4A CN115449064B (en) | 2022-11-10 | 2022-11-10 | Artificial quartz stone unsaturated polyester resin and preparation method thereof |
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| CN202211402468.4A CN115449064B (en) | 2022-11-10 | 2022-11-10 | Artificial quartz stone unsaturated polyester resin and preparation method thereof |
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| CN115449064B true CN115449064B (en) | 2023-03-24 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4152511A (en) * | 1975-10-25 | 1979-05-01 | Dynamit Nobel Aktiengesellschaft | Linear or unsaturated polyesters prepared from bis-carbalkoxy compounds |
| FR2458563A1 (en) * | 1979-06-05 | 1981-01-02 | Owens Corning Fiberglass Corp | Unsatd. polyester prodn. from glycol (terephthalate oligomers) - formed as waste prods. in polyethylene terephthalate prodn. |
| CN112358577A (en) * | 2021-01-06 | 2021-02-12 | 湖北旺林新材料科技有限公司 | Modified quartz stone resin and preparation method and application thereof |
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2022
- 2022-11-10 CN CN202211402468.4A patent/CN115449064B/en active Active
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Denomination of invention: An artificial quartz stone unsaturated polyester resin and its preparation method Effective date of registration: 20231026 Granted publication date: 20230324 Pledgee: Industrial and Commercial Bank of China Limited Jingmen Duodao Branch Pledgor: Hubei Wanglin New Material Technology Co.,Ltd. Registration number: Y2023980062557 |