CN109824829A - Sheet molding compound high-intensity and high-tenacity unsaturated polyester resin and preparation method thereof - Google Patents
Sheet molding compound high-intensity and high-tenacity unsaturated polyester resin and preparation method thereof Download PDFInfo
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- CN109824829A CN109824829A CN201910113787.5A CN201910113787A CN109824829A CN 109824829 A CN109824829 A CN 109824829A CN 201910113787 A CN201910113787 A CN 201910113787A CN 109824829 A CN109824829 A CN 109824829A
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- 239000003677 Sheet moulding compound Substances 0.000 title claims abstract description 42
- 229920006337 unsaturated polyester resin Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 32
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims abstract description 21
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims abstract description 16
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims abstract description 15
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZJTLZYDQJHKRMQ-UHFFFAOYSA-N menadiol Chemical compound C1=CC=CC2=C(O)C(C)=CC(O)=C21 ZJTLZYDQJHKRMQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000004031 fumaroyl group Chemical group C(\C=C\C(=O)*)(=O)* 0.000 claims abstract description 14
- 239000004615 ingredient Substances 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 229920006305 unsaturated polyester Polymers 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 101000823778 Homo sapiens Y-box-binding protein 2 Proteins 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 6
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 6
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000004383 yellowing Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 isobutyl ester Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Sheet molding compound high-intensity and high-tenacity unsaturated polyester resin and preparation method thereof, the present invention relates to high-molecular compound preparation technical fields.It is made of following parts by weight ingredient: 200-250 parts of tetrahydrophthalic anhydride, 500-550 parts of M-phthalic acid, 4750-4950 parts of fumaroyl, 2- methyl-1,750-850 parts of 3-propanediol, 3750-3850 parts of neopentyl glycol, 700-900 parts of styrene, 4000-4200 parts of Isobutyl methacrylate, 2-5 parts of quinhydrones, 2-5 parts of methylnaphthohydroquinone, 2-6 parts of 2,6-di-tert-butyl p-cresol.Prepared unsaturated polyester resin realizes that its SMC product has excellent resistance to yellowing and water resistance.Prepared unsaturated polyester resin realizes that the high activity of resin and resin heat distortion temperature reach 100 DEG C or more.
Description
Technical field
The present invention relates to high-molecular compound preparation technical fields, and in particular to sheet molding compound with high-intensity and high-tenacity not
Saturated polyester resin and preparation method thereof.
Background technique
Sheet molding compound SMC(Sheet molding compond) it with unsaturated polyester resin is multi-functional group high score
Sub- compound is dissolved in the obtained mixture solution of activated monomer, is dispersed with insatiable hunger on the unsaturated polyester (UP) main chain in the solution
And double bond, the end of the chain of unsaturated polyester (UP) main chain are also dispersed with carboxyl or hydroxyl.Sheet mould is produced using unsaturated polyester resin
Plastics SMC material has excellent engineering mechanics performance, electrical insulation capability, heat steady by hot-forming obtained SMC product
Qualitative energy, corrosion resistance etc..SMC product has wide range of applications, and is mainly used in electrical industry, auto industry, high-speed iron
The fields such as road and rolling stock, Communication Engineering, electrical equipment, bathroom facility, construction material.Currently, domestic SMC technology and
Technique comparative maturity, some products and technology already close to or reach advanced world standards.
Sheet molding compound SMC is one for pasting dipping chopped strand or glass fabric etc. by unsaturated polyester resin and obtaining
Kind of preimpregnation material, has that structure design is strong, high production efficiency, hazardous waste using the production that SMC material carries out molded article
The features such as discharge is few.
There is the situation of water resistance, weather resistance deficiency, main table in the application of high-end bathroom product in SMC material
It is now SMC bathroom product all the year round in use, there is obvious water-line, and the obvious yellowing of association, seriously affects product
Aesthetic effect, development and good application of the sluggish SMC material in sanitary ware industry.Sheet molding compound SMC unsaturated polyester resin
It is one of the key component for producing SMC material, the water resistance and resistant to yellowing of unsaturated polyester resin directly affect SMC product
Correlated performance.
Summary of the invention
In view of the defects and deficiencies of the prior art, the present invention intends to provide a kind of structure is simple, design rationally, make
With convenient sheet molding compound high-intensity and high-tenacity unsaturated polyester resin and preparation method thereof, prepared unsaturated polyester (UP)
Resin realizes that its SMC product has excellent resistance to yellowing and water resistance.Prepared unsaturated polyester resin realizes resin
High activity and resin heat distortion temperature reach 100 DEG C or more.
To achieve the above object, sheet molding compound of the present invention high-intensity and high-tenacity unsaturated polyester resin, it
It is made of following parts by weight ingredient: 200-250 parts of tetrahydrophthalic anhydride, 500-550 parts of M-phthalic acid, fumaroyl 4750-
4950 parts, 2- methyl-1,750-850 parts of 3-propanediol, 3750-3850 parts of neopentyl glycol, 700-900 parts of styrene, methyl-prop
4000-4200 parts of olefin(e) acid isobutyl ester, 2-5 parts of quinhydrones, 2-5 parts of methylnaphthohydroquinone, 2-6 parts of DBPC 2,6 ditertiary butyl p cresol.
Further, sheet molding compound high-intensity and high-tenacity unsaturated polyester resin, it is by following parts by weight
At being grouped as: 220-230 parts of tetrahydrophthalic anhydride, 520-530 parts of M-phthalic acid, 4840-4860 parts of fumaroyl, 2- first
Base -790-810 parts of 1,3-PD, 3790-3810 parts of neopentyl glycol, 790-810 parts of styrene, Isobutyl methacrylate
4050-4150 parts, 3-4 parts of quinhydrones, 3-4 parts of methylnaphthohydroquinone, 4-5 parts of DBPC 2,6 ditertiary butyl p cresol.
Further, sheet molding compound high-intensity and high-tenacity unsaturated polyester resin, it is by following parts by weight
At being grouped as: 220-225 parts of tetrahydrophthalic anhydride, 520-525 parts of M-phthalic acid, 4850-4855 parts of fumaroyl, 2- first
Base -800-805 parts of 1,3-PD, 3800-3805 parts of neopentyl glycol, 800-805 parts of styrene, Isobutyl methacrylate
4100-4150 parts, 3.5-4 parts of quinhydrones, 3.5-4 parts of methylnaphthohydroquinone, 4.5-5 parts of DBPC 2,6 ditertiary butyl p cresol.
The preparation method of sheet molding compound of the present invention high-intensity and high-tenacity unsaturated polyester resin, step is such as
Under:
1, under conditions of nitrogen flow 2-6m3/h, M-phthalic acid, tetrahydrophthalic anhydride, 2- methyl 1,3 third are added into reaction kettle
Glycol, neopentyl glycol are warming up to 180-210 DEG C, and reaction to acid value reaches 8-12mgKOH/g；
2, material is cooled to 140-150 DEG C, adds fumaroyl, methylnaphthohydroquinone is warming up to 190-210 DEG C, and reaction is extremely
Acid value reaches 60-65 mgKOH/g, and increasing nitrogen flow is 30-40m3/h, and the reaction was continued to 30-35 mgKOH/g；Close nitrogen
Gas carries out reaction kettle to vacuumize 30-40min, stops vacuumizing, and continues to be passed through nitrogen, keeps nitrogen flow 36-40m3/h,
Reaction reaches 20-24mgKOH/g to acid value, is cooled to 160-180 DEG C, obtains unsaturated polyester (UP)；
3, above-mentioned prepared unsaturated polyester (UP) is added to styrene, Isobutyl methacrylate, quinhydrones, 2,6 di-t-butyls
It in the mixture of paracresol, is sufficiently uniformly dissolved, is cooled to 40-50 DEG C.
After adopting the above structure, the invention has the following beneficial effects:
1, using 1,3 propylene glycol of 2- methyl and neopentyl glycol, diethylene glycol, dipropylene glycol are abandoned, eliminates ehter bond poor water resistance
Hidden danger realizes the excellent water resistance of SMC material；
2, in the relatively low of the endpoint acid number control of unsaturated polyester (UP) synthesis, make unsaturated polyester (UP) molecular weight with higher, it is real
Resin water resistance is now promoted, meanwhile, also realize that resin has excellent thickening capabilities；
3, most of styrene is substituted using Isobutyl methacrylate, realizes the excellent resistant to yellowing of resin；
4, prepared resin is suitble to produce high-grade SMC bathroom product, bloom decorative building material.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention without any creative labor, may be used also for those of ordinary skill in the art
To obtain other drawings based on these drawings.
Fig. 1 is the high-intensity and high-tenacity unsaturated polyester resin of sheet molding compound obtained by embodiment one to embodiment five
Performance test table.
Specific embodiment
The present invention will be further described below with reference to the drawings.
Referring to as shown in Figure 1, sheet molding compound high intensity and high ductility described in present embodiment (embodiment one)
Property unsaturated polyester resin, it is made of following parts by weight ingredient: 225 parts of tetrahydrophthalic anhydride, 525 parts of M-phthalic acid, trans- fourth
4950 parts of enedioic acid, 2- methyl-1,800 parts of 3-propanediol, 3800 parts of neopentyl glycol, 800 parts of styrene, isobutyl
4100 parts of ester, 3 parts of quinhydrones, 4 parts of methylnaphthohydroquinone, 5 parts of DBPC 2,6 ditertiary butyl p cresol.
Preparation method of the sheet molding compound described in the present embodiment with high-intensity and high-tenacity unsaturated polyester resin, step
It is as follows:
1, under conditions of nitrogen flow 2-6m3/h, M-phthalic acid, tetrahydrophthalic anhydride, 2- methyl 1,3 third are added into reaction kettle
Glycol, neopentyl glycol are warming up to 180-210 DEG C, and reaction to acid value reaches 8-12mgKOH/g；
2, material is cooled to 140-150 DEG C, adds fumaroyl, methylnaphthohydroquinone is warming up to 190-210 DEG C, and reaction is extremely
Acid value reaches 60-65 mgKOH/g, and increasing nitrogen flow is 30-40m3/h, and the reaction was continued to 30-35 mgKOH/g；Close nitrogen
Gas carries out reaction kettle to vacuumize 30-40min, stops vacuumizing, and continues to be passed through nitrogen, keeps nitrogen flow 36-40m3/h,
Reaction reaches 20-24mgKOH/g to acid value, is cooled to 160-180 DEG C, obtains unsaturated polyester (UP)；
3, above-mentioned prepared unsaturated polyester (UP) is added to styrene, Isobutyl methacrylate, quinhydrones, 2,6 di-t-butyls
It in the mixture of paracresol, is sufficiently uniformly dissolved, is cooled to 40-50 DEG C.
Embodiment two:
The high-intensity and high-tenacity unsaturated polyester resin of sheet molding compound described in the present embodiment, it is by following parts by weight ingredient
Composition: 225 parts of tetrahydrophthalic anhydride, 525 parts of M-phthalic acid, 4750 parts of fumaroyl, 2- methyl-1,3-propanediol 800
Part, 3800 parts of neopentyl glycol, 800 parts of styrene, 4100 parts of Isobutyl methacrylate, 3 parts of quinhydrones, 4 parts of methylnaphthohydroquinone,
5 parts of DBPC 2,6 ditertiary butyl p cresol；Preparation method is the same as example 1.
Embodiment three:
The high-intensity and high-tenacity unsaturated polyester resin of sheet molding compound described in the present embodiment, it is by following parts by weight ingredient
Composition: 225 parts of tetrahydrophthalic anhydride, 525 parts of M-phthalic acid, 4850 parts of fumaroyl, 2- methyl-1,3-propanediol 850
Part, 3750 parts of neopentyl glycol, 800 parts of styrene, 4100 parts of Isobutyl methacrylate, 3 parts of quinhydrones, 4 parts of methylnaphthohydroquinone,
5 parts of DBPC 2,6 ditertiary butyl p cresol；Preparation method is the same as example 1.
Example IV:
The high-intensity and high-tenacity unsaturated polyester resin of sheet molding compound described in the present embodiment, it is by following parts by weight ingredient
Composition: 200 parts of tetrahydrophthalic anhydride, 550 parts of M-phthalic acid, 4850 parts of fumaroyl, 2- methyl-1,800 parts of 3-propanediol,
3800 parts of neopentyl glycol, 800 parts of styrene, 4100 parts of Isobutyl methacrylate, 3 parts of quinhydrones, 4 parts of methylnaphthohydroquinone, 2,6-
5 parts of di-tert-butyl p-cresol；Preparation method is the same as example 1.
Embodiment five:
The high-intensity and high-tenacity unsaturated polyester resin of sheet molding compound described in the present embodiment, it is by following parts by weight ingredient
Composition: 225 parts of tetrahydrophthalic anhydride, 525 parts of M-phthalic acid, 4850 parts of fumaroyl, 2- methyl-1,800 parts of 3-propanediol,
3800 parts of neopentyl glycol, 800 parts of styrene, 4100 parts of Isobutyl methacrylate, 3 parts of quinhydrones, 4 parts of methylnaphthohydroquinone, 2,6-
5 parts of di-tert-butyl p-cresol；Preparation method is the same as example 1.
The above is only used to illustrate the technical scheme of the present invention and not to limit it, and those of ordinary skill in the art are to this hair
The other modifications or equivalent replacement that bright technical solution is made, as long as it does not depart from the spirit and scope of the technical scheme of the present invention,
It is intended to be within the scope of the claims of the invention.
Claims (4)
1. sheet molding compound high-intensity and high-tenacity unsaturated polyester resin, it is characterised in that: it is by following parts by weight ingredient group
At: 200-250 parts of tetrahydrophthalic anhydride, 500-550 parts of M-phthalic acid, 4750-4950 parts of fumaroyl, 2- methyl-1,3-
750-850 parts of propylene glycol, 3750-3850 parts of neopentyl glycol, 700-900 parts of styrene, Isobutyl methacrylate 4000-
4200 parts, 2-5 parts of quinhydrones, 2-5 parts of methylnaphthohydroquinone, 2-6 parts of DBPC 2,6 ditertiary butyl p cresol.
2. sheet molding compound according to claim 1 high-intensity and high-tenacity unsaturated polyester resin, it is characterised in that: institute
The sheet molding compound stated high-intensity and high-tenacity unsaturated polyester resin, it is made of following parts by weight ingredient: tetrahydrophthalic anhydride
220-230 parts, 520-530 parts of M-phthalic acid, 4840-4860 parts of fumaroyl, 2- methyl-1,3-propanediol 790-
810 parts, 3790-3810 parts of neopentyl glycol, 790-810 parts of styrene, 4050-4150 parts of Isobutyl methacrylate, quinhydrones
3-4 parts, 3-4 parts of methylnaphthohydroquinone, 4-5 parts of DBPC 2,6 ditertiary butyl p cresol.
3. sheet molding compound according to claim 1 high-intensity and high-tenacity unsaturated polyester resin, it is characterised in that: institute
The sheet molding compound stated high-intensity and high-tenacity unsaturated polyester resin, it is made of following parts by weight ingredient: tetrahydrophthalic anhydride
220-225 parts, 520-525 parts of M-phthalic acid, 4850-4855 parts of fumaroyl, 2- methyl-1,3-propanediol 800-
805 parts, 3800-3805 parts of neopentyl glycol, 800-805 parts of styrene, 4100-4150 parts of Isobutyl methacrylate, quinhydrones
3.5-4 parts, 3.5-4 parts of methylnaphthohydroquinone, 4.5-5 parts of DBPC 2,6 ditertiary butyl p cresol.
4. the sheet molding compound preparation method of high-intensity and high-tenacity unsaturated polyester resin, it is characterised in that: its step are as follows:
(1), under conditions of nitrogen flow 2-6m3/h, M-phthalic acid, tetrahydrophthalic anhydride, 2- methyl 1,3 are added into reaction kettle
Propylene glycol, neopentyl glycol are warming up to 180-210 DEG C, and reaction to acid value reaches 8-12mgKOH/g；
(2), material is cooled to 140-150 DEG C, adds fumaroyl, methylnaphthohydroquinone is warming up to 190-210 DEG C, reaction
Reach 60-65 mgKOH/g to acid value, increasing nitrogen flow is 30-40m3/h, and the reaction was continued to 30-35 mgKOH/g；It closes
Nitrogen carries out reaction kettle to vacuumize 30-40min, stops vacuumizing, and continues to be passed through nitrogen, keeps nitrogen flow 36-40m3/
H, reaction reach 20-24mgKOH/g to acid value, are cooled to 160-180 DEG C, obtain unsaturated polyester (UP)；
(3), above-mentioned prepared unsaturated polyester (UP) is added to styrene, Isobutyl methacrylate, quinhydrones, 2,6 2 tertiary fourths
It in the mixture of base paracresol, is sufficiently uniformly dissolved, is cooled to 40-50 DEG C.
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| CN113087853A (en) * | 2021-04-26 | 2021-07-09 | 宜兴市兴合树脂有限公司 | Pultrusion resin for producing frame structure for shallow sea cultivation |
| CN113929887A (en) * | 2021-09-08 | 2022-01-14 | 福建省南安市华龙树脂有限公司 | Unsaturated polyester resin applied to continuously winding glass fiber reinforced plastic pipeline and preparation method thereof |
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| CN113929887A (en) * | 2021-09-08 | 2022-01-14 | 福建省南安市华龙树脂有限公司 | Unsaturated polyester resin applied to continuously winding glass fiber reinforced plastic pipeline and preparation method thereof |
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Application publication date: 20190531 |