CN109181255A - A kind of flame-retarded unsaturated polyester resin glass reinforced plastic - Google Patents
A kind of flame-retarded unsaturated polyester resin glass reinforced plastic Download PDFInfo
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- CN109181255A CN109181255A CN201810972937.3A CN201810972937A CN109181255A CN 109181255 A CN109181255 A CN 109181255A CN 201810972937 A CN201810972937 A CN 201810972937A CN 109181255 A CN109181255 A CN 109181255A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a kind of flame-retarded unsaturated polyester resin glass reinforced plastic, the raw material comprising following parts by weight: 40-50 parts of phosphor-containing flame-proof unsaturated polyester resin, 5-15 parts of phenolic resin, 10-20 parts of polyvinyl chloride resin, 2-5 parts of calcium stearate, 2-5 parts of calcium carbonate, 2-5 parts of aluminium hydroxide, 1-5 parts of glass microballoon, 2-6 parts of ceramic powder, 2-6 parts of silicon powder, 8-15 parts of reinforcing material, 1-5 parts of macromolecule toughness agent.A kind of flame-retarded unsaturated polyester resin glass reinforced plastic proposed by the present invention while the unsaturated polyester resin glass reinforced plastic is effectively improved fire-retardant and toughness properties, also has environmental protection, safe advantage.
Description
Technical field
The present invention relates to glass fibre reinforced plastics technology field more particularly to a kind of flame-retarded unsaturated polyester resin glass reinforced plastics.
Background technique
Polyester resin can be divided into two kinds: one is saturated polyester resin, there is no non-aromatic unsaturated bond in molecular structure,
It is a kind of thermoplastic resin.Another kind is unsaturated polyester resin, contains non-aromatic unsaturated bond in molecular structure, has and change
Thickening property is learned, cross-linking reaction can be caused with initiator and become a kind of thermosetting plastics.Mechanics after unsaturated polyester resin solidification
Performance is relatively low, if it is many excellent can to form high, resistant to chemical etching, electrical isolation of a kind of light weight, intensity etc. with glass fiber reinforcement
The substance of benign energy, is commonly called as glass reinforced plastic.
Glass reinforced plastic is a kind of composite material, it is using resin as matrix, and glass fibre is combined for reinforcing material, also referred to as
For fiberglass reinforced plastics, mainly have the following characteristics that light high-strength, tensile strength is 4-6 times of ordinary steel；Corrosion-resistant,
Anti-aging, service life is 50 years；It is easily molded, designability is strong；There are good insulating properties and heat resistance.
With the continuous development and extension of glass reinforced plastic industry, glass-reinforced plastic boat and cabin cover of wind power generator etc. are large-scale in recent years
Glass fiber reinforced plastics product, which also obtains, vigorously to be developed.At the same time, the matter of market and user to glass reinforced plastic unsaturated polyester resin
Higher requirements are also raised for amount.But traditional glass reinforced plastic unsaturated polyester resin is due to being easy to burning, poor toughness etc.
Disadvantage can only be suitble to make small-sized glass fiber reinforced plastics product；On the other hand, volatile toxic styrene in unsaturated polyester resin
Very big harm can be generated to the health of construction personnel, styrene is dispersed into air, will also result in serious environmental pollution.This
When molding glass reinforced plastic made as raw material using traditional unsaturated polyester resin be not able to satisfy the requirement such as fire-retardant and environmentally friendly necessarily.
Summary of the invention
The problem of based on background technique, the invention proposes a kind of flame-retarded unsaturated polyester resin glass reinforced plastic, institutes
While stating unsaturated polyester resin glass reinforced plastic and be effectively improved fire-retardant and toughness properties, also there is environmental protection, safe advantage.
A kind of flame-retarded unsaturated polyester resin glass reinforced plastic proposed by the present invention, the raw material comprising following parts by weight: phosphorous
40-50 parts of flame-retarded unsaturated polyester resin, 5-15 parts of phenolic resin, 10-20 parts of polyvinyl chloride resin, 2-5 parts of calcium stearate, calcium carbonate
2-5 parts, 2-5 parts of aluminium hydroxide, 1-5 parts of glass microballoon, 2-6 parts of ceramic powder, 2-6 parts of silicon powder, 8-15 parts of reinforcing material, high score
1-5 parts of sub- toughness agent；
The method for preparing the flame-retarded unsaturated polyester resin glass reinforced plastic include: by phosphor-containing flame-proof unsaturated polyester resin,
After phenolic resin, polyvinyl chloride resin mixing, mixture A is stirred to get；Calcium stearate, calcium carbonate, hydroxide are added into mixture A
Aluminium, glass microballoon, ceramic powder, silicon powder, reinforcing material mixing, are stirred to react 1.5-2h after being warming up to 90-100 DEG C, after of continuing rising
Temperature is cooled to room temperature to 2-3h is stirred to react after 120-130 DEG C, obtains mixture B；Macromolecule toughness is added into mixture B
Agent mixing, stirs to get the flame-retarded unsaturated polyester resin glass reinforced plastic.
Preferably, the phosphor-containing flame-proof unsaturated polyester resin is to prepare to be formed by following technique: by weight will be suitable
20-30 parts of anhydride maleique, 30-40 parts of phthalic anhydride, 45-55 parts of 1,2-PD mixings, are heated under nitrogen protection
Melting, be stirred to react 2-4h after being warming up to 150-160 DEG C, after being continuously heating to 190-200 DEG C insulation reaction to system acid value not
Become, phosphorous vinyl monomer 30-40 parts, 0.01-0.1 parts of hydroquinone, peroxidating two are sequentially added after being cooled to 90-100 DEG C
0.5-2 parts of benzoyl, obtain the phosphor-containing flame-proof unsaturated polyester resin.
Preferably, the phosphorous vinyl monomer is to prepare to be formed by following technique: under nitrogen protection, by molar part
It will be dissolved in 1-2 parts of addition methylene chloride of fumaric acid dibutylene glycol ester completely, three second be added after cooling 0.5-1h in ice-water bath
2.2-2.5 parts of amine, the dichloromethane solution dissolved with 2.2-2.6 parts of diphenyl phosphorus chloride is added dropwise under agitation, under ice-water bath
Be stirred to react 5-8h, continue to be stirred to react 15-20h after being warming up to 30-40 DEG C, filter and remove triethylamine salt, successively with dilute hydrochloric acid,
Sodium bicarbonate and saturated sodium chloride solution are washed, and are removed solvent, are obtained the phosphorous vinyl monomer.
Preferably, the fumaric acid dibutylene glycol ester is to prepare to be formed by following technique: under nitrogen protection, general mole
Than for 1:3-5 fumaric acid and 1,4-butanediol be added in toluene, be stirred to react 5-7h after being warming up to 90-100 DEG C, remove molten
It is recrystallized after agent with the mixed solution of methylene chloride and methanol, obtains the fumaric acid dibutylene glycol ester.
Preferably, the reinforcing material is one of glass fibre, carbon fiber or plant fiber.
Preferably, the macromolecule toughness agent is Styrene-Butadiene-Styrene Block Copolymer, ethylene-acrylic acid
One of methyl terpolymer, ethyl-vinyl acetate random copolymer.
Preferably, the method for preparing the flame-retarded unsaturated polyester resin glass reinforced plastic includes: to gather phosphor-containing flame-proof unsaturation
After ester resin, phenolic resin, polyvinyl chloride resin mixing, 0.15-0.3h is stirred under the rate of 500-1000r/min, obtains mixture
A；It is mixed that calcium stearate, calcium carbonate, aluminium hydroxide, glass microballoon, ceramic powder, silicon powder, reinforcing material are added into mixture A
It closes, is stirred to react 1.6-1.8h after being warming up to 93-98 DEG C, 2.2-2.7h is stirred to react after being continuously heating to 125-128 DEG C, it is cooling
To room temperature, mixture B is obtained；Macromolecule toughness agent mixing is added into mixture B, first under the rate of 3000-4000r/min
High-speed stirred 0.1-0.2h, then 0.3-0.5h is stirred at low speed under the rate of 500-1000r/min, obtain the fire-retardant unsaturation
Polyester resin glass reinforced plastic.
In the present invention, the phosphor-containing flame-proof unsaturated polyester resin is by synthesizing one kind by fumaric acid dibutylene glycol ester and two
The phosphorous vinyl monomer that tetraphenylphosphonium chloride phosphorus synthesizes obtains to substitute styrene with unsaturated polyester resin matrix crosslinking curing
It arrives, on the one hand avoid the inflammable of styrene and will cause serious environmental pollution defect, it on the other hand then can be by P elements
Inflammable on unsaturated polyester (UP) skeleton by chemical method, oxygen index (OI) is increased to 35% or more from 19%, and vertical combustion is logical
Cross UL94-V0 grades；In addition, phenolic resin is added for cooperation and polyvinyl chloride resin carries out enhancing modification, oxidation resistent susceptibility is good, heat-resisting quantity
It can further increase, chemical stability is good.The macromolecule toughness agent added in the present invention can be improved the tough of glass reinforced plastic entirety
Property, it further prolongs its service life, is suitble to use under rugged environment.I.e. compared with prior art, the present invention prepares work
Skill is simple, and preparation process is environment friendly and pollution-free, and glass-reinforced plastic material obtained has superior fire-retardant, high temperature resistance, while also having
There are the characteristics of high tenacity, long service life.
Specific embodiment
In the following, technical solution of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of flame-retarded unsaturated polyester resin glass reinforced plastic, the raw material comprising following parts by weight: phosphor-containing flame-proof unsaturation is poly-
40 parts of ester resin, 15 parts of phenolic resin, 10 parts of polyvinyl chloride resin, 5 parts of calcium stearate, 2 parts of calcium carbonate, 5 parts of aluminium hydroxide, glass are micro-
1 part of pearl, 6 parts of ceramic powder, 2 parts of silicon powder, 15 parts of glass fibre, 1 part of Styrene-Butadiene-Styrene Block Copolymer；
Wherein, the phosphor-containing flame-proof unsaturated polyester resin is to prepare to be formed by following technique: under nitrogen protection, will
Molar ratio is that the fumaric acid of 1:3 and 1,4-butanediol are added in toluene, and 5h is stirred to react after being warming up to 100 DEG C, removes solvent
It is recrystallized afterwards with the mixed solution of methylene chloride and methanol, obtains fumaric acid dibutylene glycol ester；Under nitrogen protection, it massages
You will dissolve completely at part in 1 part of addition methylene chloride of the fumaric acid dibutylene glycol ester, be added three after cooling 1h in ice-water bath
2.2 parts of ethamine, the dichloromethane solution dissolved with 2.6 parts of diphenyl phosphorus chloride is added dropwise under agitation, is stirred under ice-water bath anti-
5h is answered, continues to be stirred to react 15h after being warming up to 40 DEG C, filters and remove triethylamine salt, successively use dilute hydrochloric acid, sodium bicarbonate and saturation
Sodium chloride solution is washed, and is removed solvent, is obtained phosphorous vinyl monomer；Again by weight by 20 parts of maleic anhydride,
40 parts of phthalic anhydride, 45 parts of 1,2-PD mixings, heating melting, is stirred anti-after being warming up to 160 DEG C under nitrogen protection
2h is answered, insulation reaction is constant to system acid value after being continuously heating to 200 DEG C, and phosphorous vinyl list is sequentially added after being cooled to 90 DEG C
40 parts of body, 0.01 part of hydroquinone, 2 parts of dibenzoyl peroxide, obtain the phosphor-containing flame-proof unsaturated polyester resin.
The method for preparing above-mentioned flame-retarded unsaturated polyester resin glass reinforced plastic include: by phosphor-containing flame-proof unsaturated polyester resin,
After phenolic resin, polyvinyl chloride resin mixing, 0.3h is stirred under the rate of 500r/min, obtains mixture A；It is added into mixture A
Calcium stearate, calcium carbonate, aluminium hydroxide, glass microballoon, ceramic powder, silicon powder, glass fibre mixing, are stirred after being warming up to 90 DEG C
2h is reacted, 3h is stirred to react after being continuously heating to 120 DEG C, is cooled to room temperature, obtain mixture B；Benzene second is added into mixture B
Alkene-butadiene-styrene block copolymer mixing, the first high-speed stirred 0.2h under the rate of 3000r/min, then in 500r/min
Rate under stir at low speed 0.5h, obtain the flame-retarded unsaturated polyester resin glass reinforced plastic.
Embodiment 2
A kind of flame-retarded unsaturated polyester resin glass reinforced plastic, the raw material comprising following parts by weight: phosphor-containing flame-proof unsaturation is poly-
50 parts of ester resin, 5 parts of phenolic resin, 20 parts of polyvinyl chloride resin, 2 parts of calcium stearate, 5 parts of calcium carbonate, 2 parts of aluminium hydroxide, glass microballoon
5 parts, 2 parts of ceramic powder, 6 parts of silicon powder, 8 parts of carbon fiber, 5 parts of ethylene-methyl acrylate copolymer；
Wherein, the phosphor-containing flame-proof unsaturated polyester resin is to prepare to be formed by following technique: by weight will be along fourth
30 parts of enedioic acid acid anhydride, 30 parts of phthalic anhydride, 55 parts of 1,2-PD mixings, heating melting, is warming up under nitrogen protection
It is stirred to react 4h after 150 DEG C, insulation reaction is constant to system acid value after being continuously heating to 190 DEG C, is cooled to after 100 DEG C and successively adds
Enter 30 parts of phosphorous vinyl monomer, 0.1 part of hydroquinone, 0.5 part of dibenzoyl peroxide, it is unsaturated to obtain the phosphor-containing flame-proof
Polyester resin；
The phosphorous vinyl monomer is to prepare to be formed by following technique: being 1:5's by molar ratio under nitrogen protection
Fumaric acid and 1,4-butanediol are added in toluene, are stirred to react 7h after being warming up to 90 DEG C, remove after solvent with methylene chloride and
The mixed solution of methanol is recrystallized, and fumaric acid dibutylene glycol ester is obtained；Under nitrogen protection, by molar part by fumaric acid two
It is dissolved in 2 parts of addition methylene chloride of butanediol ester completely, is added 2.5 parts of triethylamine after cooling 0.5h in ice-water bath, is stirring
Under the conditions of be added dropwise dissolved with 2.2 parts of diphenyl phosphorus chloride of dichloromethane solution, 8h is stirred to react under ice-water bath, after being warming up to 30 DEG C
Continue to be stirred to react 20h, filters and remove triethylamine salt, successively washed with dilute hydrochloric acid, sodium bicarbonate and saturated sodium chloride solution
It washs, removes solvent, obtain the phosphorous vinyl monomer.
The method for preparing above-mentioned flame-retarded unsaturated polyester resin glass reinforced plastic include: by phosphor-containing flame-proof unsaturated polyester resin,
After phenolic resin, polyvinyl chloride resin mixing, 0.15h is stirred under the rate of 1000r/min, obtains mixture A；Add into mixture A
Enter calcium stearate, calcium carbonate, aluminium hydroxide, glass microballoon, ceramic powder, silicon powder, carbon fiber mixing, is stirred after being warming up to 100 DEG C
Reaction 1.5h is mixed, 2h is stirred to react after being continuously heating to 130 DEG C, is cooled to room temperature, obtain mixture B；It is added into mixture B
Ethylene-methyl acrylate copolymer mixing, first the high-speed stirred 0.1h under the rate of 4000r/min, then the speed in 1000r/min
0.3h is stirred at low speed under rate, obtains the flame-retarded unsaturated polyester resin glass reinforced plastic.
Embodiment 3
A kind of flame-retarded unsaturated polyester resin glass reinforced plastic, the raw material comprising following parts by weight: phosphor-containing flame-proof unsaturation is poly-
45 parts of ester resin, 10 parts of phenolic resin, 15 parts of polyvinyl chloride resin, 3 parts of calcium stearate, 3 parts of calcium carbonate, 3 parts of aluminium hydroxide, glass are micro-
3 parts of pearl, 4 parts of ceramic powder, 4 parts of silicon powder, 11 parts of glass fibre, ethyl -3 parts of vinyl acetate random copolymer；
The phosphor-containing flame-proof unsaturated polyester resin is to prepare to be formed by following technique: by weight by maleic acid
25 parts of acid anhydride, 35 parts of phthalic anhydride, 50 parts of 1,2-PD mixings, heating melting under nitrogen protection, after being warming up to 155 DEG C
It is stirred to react 3h, insulation reaction is constant to system acid value after being continuously heating to 195 DEG C, and phosphorous second is sequentially added after being cooled to 95 DEG C
35 parts of alkenyl monomer, 0.05 part of hydroquinone, 1 part of dibenzoyl peroxide, obtain the phosphor-containing flame-proof unsaturated polyester resin；
The phosphorous vinyl monomer is to prepare to be formed by following technique: being 1:4's by molar ratio under nitrogen protection
Fumaric acid and 1,4-butanediol are added in toluene, are stirred to react 6h after being warming up to 95 DEG C, remove after solvent with methylene chloride and
The mixed solution of methanol is recrystallized, and fumaric acid dibutylene glycol ester is obtained；Under nitrogen protection, by molar part by the rich horse
It is dissolved in 1.5 parts of addition methylene chloride of sour dibutylene glycol ester completely, is added 2.3 parts of triethylamine after cooling 0.7h in ice-water bath,
The dichloromethane solution dissolved with 2.4 parts of diphenyl phosphorus chloride is added dropwise under agitation, is stirred to react 6h under ice-water bath, is warming up to
Continue to be stirred to react 17h after 35 DEG C, filter and remove triethylamine salt, successively uses dilute hydrochloric acid, sodium bicarbonate and saturated sodium chloride solution
It is washed, removes solvent, obtain the phosphorous vinyl monomer.
The method for preparing above-mentioned flame-retarded unsaturated polyester resin glass reinforced plastic include: by phosphor-containing flame-proof unsaturated polyester resin,
After phenolic resin, polyvinyl chloride resin mixing, 0.2h is stirred under the rate of 700r/min, obtains mixture A；It is added into mixture A
Calcium stearate, calcium carbonate, aluminium hydroxide, glass microballoon, ceramic powder, silicon powder, glass fibre mixing, are stirred after being warming up to 93 DEG C
1.8h is reacted, 2.7h is stirred to react after being continuously heating to 125 DEG C, is cooled to room temperature, obtain mixture B；It is added into mixture B
Ethyl-vinyl acetate random copolymer mixing, the first high-speed stirred 0.15h under the rate of 3500r/min, then in 700r/min
Rate under stir at low speed 0.4h, obtain the flame-retarded unsaturated polyester resin glass reinforced plastic.
Embodiment 4
A kind of flame-retarded unsaturated polyester resin glass reinforced plastic, the raw material comprising following parts by weight: phosphor-containing flame-proof unsaturation is poly-
48 parts of ester resin, 8 parts of phenolic resin, 16 parts of polyvinyl chloride resin, 4 parts of calcium stearate, 4 parts of calcium carbonate, 4 parts of aluminium hydroxide, glass microballoon
2 parts, 3 parts of ceramic powder, 5 parts of silicon powder, 12 parts of plant fiber, ethyl -3 parts of vinyl acetate random copolymer；
The phosphor-containing flame-proof unsaturated polyester resin is to prepare to be formed by following technique: by weight by maleic acid
28 parts of acid anhydride, 36 parts of phthalic anhydride, 52 parts of 1,2-PD mixings, heating melting under nitrogen protection, after being warming up to 158 DEG C
It is stirred to react 3.5h, insulation reaction is constant to system acid value after being continuously heating to 198 DEG C, sequentially adds after being cooled to 96 DEG C phosphorous
36 parts of vinyl monomer, 0.06 part of hydroquinone, 1.5 parts of dibenzoyl peroxide, obtain the phosphor-containing flame-proof unsaturated polyester (UP)
Resin；
The phosphorous vinyl monomer is to prepare to be formed by following technique: being 1:3.5 by molar ratio under nitrogen protection
Fumaric acid and 1,4-butanediol be added in toluene, be stirred to react 6.5h after being warming up to 98 DEG C, use dichloromethane after removing solvent
The mixed solution of alkane and methanol is recrystallized, and fumaric acid dibutylene glycol ester is obtained；It under nitrogen protection, will be described by molar part
It is dissolved in 1.6 parts of addition methylene chloride of fumaric acid dibutylene glycol ester completely, triethylamine 2.4 is added after cooling 0.8h in ice-water bath
Part, the dichloromethane solution dissolved with 2.3 parts of diphenyl phosphorus chloride is added dropwise under agitation, is stirred to react 7h under ice-water bath, rises
Temperature is filtered and removes triethylamine salt, successively use dilute hydrochloric acid, sodium bicarbonate and saturated sodium-chloride to continuing after 36 DEG C to be stirred to react 18h
Solution is washed, and is removed solvent, is obtained the phosphorous vinyl monomer.
The method for preparing above-mentioned flame-retarded unsaturated polyester resin glass reinforced plastic include: by phosphor-containing flame-proof unsaturated polyester resin,
After phenolic resin, polyvinyl chloride resin mixing, 0.25h is stirred under the rate of 800r/min, obtains mixture A；Add into mixture A
Enter calcium stearate, calcium carbonate, aluminium hydroxide, glass microballoon, ceramic powder, silicon powder, plant fiber mixing, is stirred after being warming up to 98 DEG C
Reaction 1.6h is mixed, 2.2h is stirred to react after being continuously heating to 128 DEG C, is cooled to room temperature, obtain mixture B；Add into mixture B
Enter ethyl-vinyl acetate random copolymer mixing, first the high-speed stirred 0.12h under the rate of 3600r/min, then in 800r/
0.35h is stirred at low speed under the rate of min, obtains the flame-retarded unsaturated polyester resin glass reinforced plastic.
Flame-retarded unsaturated polyester resin glass reinforced plastic prepared by above-described embodiment 1-4 carries out anti-flammability and impact flexibility is surveyed
Examination, as a result as shown in the table:
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (7)
1. a kind of flame-retarded unsaturated polyester resin glass reinforced plastic, which is characterized in that the raw material comprising following parts by weight: phosphor-containing flame-proof
40-50 parts of unsaturated polyester resin, 5-15 parts of phenolic resin, 10-20 parts of polyvinyl chloride resin, 2-5 parts of calcium stearate, calcium carbonate 2-5
Part, 2-5 parts of aluminium hydroxide, 1-5 parts of glass microballoon, 2-6 parts of ceramic powder, 2-6 parts of silicon powder, 8-15 parts of reinforcing material, macromolecule
1-5 parts of toughness agent；
The method for preparing the flame-retarded unsaturated polyester resin glass reinforced plastic includes: by phosphor-containing flame-proof unsaturated polyester resin, phenolic aldehyde
After resin, polyvinyl chloride resin mixing, mixture A is stirred to get；Calcium stearate, calcium carbonate, aluminium hydroxide, glass are added into mixture A
Glass microballon, ceramic powder, silicon powder, reinforcing material mixing, are stirred to react 1.5-2h after being warming up to 90-100 DEG C, are continuously heating to
It is stirred to react 2-3h after 120-130 DEG C, is cooled to room temperature, obtains mixture B；It is mixed that the agent of macromolecule toughness is added into mixture B
It closes, stirs to get the flame-retarded unsaturated polyester resin glass reinforced plastic.
2. flame-retarded unsaturated polyester resin glass reinforced plastic according to claim 1, which is characterized in that the phosphor-containing flame-proof insatiable hunger
It is to prepare to be formed by following technique with polyester resin: by weight by 20-30 parts of maleic anhydride, phthalic anhydride
30-40 parts, 45-55 parts of 1,2-PD mixings, heating melting, is stirred to react after being warming up to 150-160 DEG C under nitrogen protection
2-4h, insulation reaction is constant to system acid value after being continuously heating to 190-200 DEG C, sequentially adds after being cooled to 90-100 DEG C phosphorous
30-40 parts of vinyl monomer, 0.01-0.1 parts of hydroquinone, 0.5-2 parts of dibenzoyl peroxide, obtain the phosphor-containing flame-proof not
Saturated polyester resin.
3. flame-retarded unsaturated polyester resin glass reinforced plastic according to claim 2, which is characterized in that in S1, the phosphorous second
Alkenyl monomer is to prepare to be formed by following technique: under nitrogen protection, being added 1-2 parts of fumaric acid dibutylene glycol ester by molar part
Enter and dissolved in methylene chloride completely, is added triethylamine 2.2-2.5 parts after cooling 0.5-1h in ice-water bath, drips under agitation
Solubilization has 2.2-2.6 parts of diphenyl phosphorus chloride of dichloromethane solution, is stirred to react 5-8h under ice-water bath, is warming up to 30-40 DEG C
After continue to be stirred to react 15-20h, filter and remove triethylamine salt, successively with dilute hydrochloric acid, sodium bicarbonate and saturated sodium chloride solution into
Row washing, removes solvent, obtains the phosphorous vinyl monomer.
4. flame-retarded unsaturated polyester resin glass reinforced plastic according to claim 3, which is characterized in that two fourth two of fumaric acid
Alcohol ester is to prepare to be formed by following technique: under nitrogen protection, fumaric acid and 1,4-butanediol that molar ratio is 1:3-5 being added
Enter into toluene, 5-7h is stirred to react after being warming up to 90-100 DEG C, the mixed solution of methylene chloride and methanol is used after removing solvent
It is recrystallized, obtains the fumaric acid dibutylene glycol ester.
5. flame-retarded unsaturated polyester resin glass reinforced plastic according to claim 1-4, which is characterized in that the enhancing
Material is one of glass fibre, carbon fiber or plant fiber.
6. flame-retarded unsaturated polyester resin glass reinforced plastic according to claim 1-5, which is characterized in that the height
Molecule toughness agent is Styrene-Butadiene-Styrene Block Copolymer, ethylene-methyl acrylate copolymer, ethyl-second
One of enester random copolymer.
7. flame-retarded unsaturated polyester resin glass reinforced plastic according to claim 1-6, which is characterized in that described in preparation
The method of flame-retarded unsaturated polyester resin glass reinforced plastic includes: by phosphor-containing flame-proof unsaturated polyester resin, phenolic resin, polyvinyl chloride resin
After mixing, 0.15-0.3h is stirred under the rate of 500-1000r/min, obtains mixture A；Stearic acid is added into mixture A
Calcium, calcium carbonate, aluminium hydroxide, glass microballoon, ceramic powder, silicon powder, reinforcing material mixing, are stirred anti-after being warming up to 93-98 DEG C
1.6-1.8h is answered, 2.2-2.7h is stirred to react after being continuously heating to 125-128 DEG C, is cooled to room temperature, obtains mixture B；To mixed
It closes and macromolecule toughness agent mixing is added in object B, first the high-speed stirred 0.1-0.2h under the rate of 3000-4000r/min, then
0.3-0.5h is stirred at low speed under the rate of 500-1000r/min, obtains the flame-retarded unsaturated polyester resin glass reinforced plastic.
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| CN201810972937.3A CN109181255A (en) | 2018-08-24 | 2018-08-24 | A kind of flame-retarded unsaturated polyester resin glass reinforced plastic |
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Citations (8)
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Application publication date: 20190111 |