CN107974063A - Glass fiber reinforced unsaturated polyester plastic and preparation method thereof - Google Patents
Glass fiber reinforced unsaturated polyester plastic and preparation method thereof Download PDFInfo
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- CN107974063A CN107974063A CN201711323768.2A CN201711323768A CN107974063A CN 107974063 A CN107974063 A CN 107974063A CN 201711323768 A CN201711323768 A CN 201711323768A CN 107974063 A CN107974063 A CN 107974063A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/06—Unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/06—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
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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Abstract
The invention discloses a kind of glass fiber reinforced unsaturated polyester plastic and preparation method thereof.The glass fiber reinforced unsaturated polyester plastic includes the component of following parts by weight：55 65 parts of unsaturated polyester resin, 20 25 parts of low shrinkage additive, 30 50 parts of glass fibre, 25 parts of zinc stearate, 0.1 0.5 parts of calcium hydroxide, 0.5 1.5 parts of peroxidized t-butyl perbenzoate, 150 200 parts of filler；The low shrinkage additive includes polystyrene and styrene, and the mixed weight ratio of the polystyrene and styrene is 1:1‑2.Beneficial effects of the present invention are：The glass fiber reinforced unsaturated polyester plastic can reduce cubical contraction, so as to avoid because the manufacturing deficiency that moulding compound volume contraction is brought.
Description
Technical field
The present invention relates to moulding compound, more particularly to a kind of glass fiber reinforced unsaturated polyester plastic and its preparation side
Method.
Background technology
BMC material, i.e. team's moulding compound, also commonly referred to as unsaturated polyester (UP) tubular molding compound.BMC tubular molding compound has excellent
Good electric property, mechanical performance, heat resistance, chemical resistance, and adapt to various moulding process, you can meet various products
Requirement to performance, therefore increasingly liked be subject to users.
The Chinese patent of Publication No. CN102504509A discloses a kind of glass fiber reinforced unsaturated polyester plastic
And preparation method thereof.In low-voltage distribution field, for overall performance, comprehensive performance angle, which is process exhausted
Edge has higher mechanical strength, heat-resisting, resistance to height compared with the insulator that the processing of high molecular material beyond silicon rubber forms
Pressure and flame-resistant insulation performance, and with prominent ageing-resistant effect, compared with insulator made of porcelain vase, there is prominent machine
The advantage of tool performance.
But the moulding compound can influence sample size precision, produce surface not when curing with the process of volume contraction
Phenomena such as smooth, warpage, have much room for improvement.
The content of the invention
The object of the present invention is to provide a kind of glass fiber reinforced unsaturated polyester plastic.The unsaturated polyester (UP) glass is fine
Dimension enhancing moulding compound can reduce cubical contraction, so as to avoid because the manufacturing deficiency that moulding compound volume contraction is brought.
The present invention above-mentioned technical purpose technical scheme is that：
A kind of glass fiber reinforced unsaturated polyester plastic, includes the component of following parts by weight：
55-65 parts of unsaturated polyester resin
20-25 parts of low shrinkage additive
30-50 parts of glass fibre
2-5 parts of zinc stearate
0.1-0.5 parts of calcium hydroxide
0.5-1.5 parts of peroxidized t-butyl perbenzoate
150-200 parts of filler；
The low shrinkage additive includes polystyrene and styrene, and the mixed weight ratio of the polystyrene and styrene is 1:
1-2。
By using above-mentioned technical proposal, the weight of different material when herein referred mixed weight is than referring to mixing
Than.Unsaturated polyester resin is most common one kind in thermosetting resin, is by monounsaturated dicarboxylic acid, unsaturated dibasic acid and binary
The linear high-molecular compound with ester bond and unsaturated double-bond that alcohol polycondensation forms.The both ends of unsaturated polyester resin respectively carry
Carboxyl and hydroxyl.Unsaturated polyester resin has higher stretching, bending, compression equal strength, water-fast, diluted acid, the performance of diluted alkaline
Preferably, the poor performance of organic solvent-resistant, dielectric properties are good.Low shrinkage additive is gathered by partial relaxation four directions planted agent's force compensating
Close and shrink, so as to reach the effect for reducing moulding compound shrinking percentage.Polystyrene and styrene are in two-phase in unsaturated polyester resin
System, using the expanded by heating of resin, suppresses the cure shrinkage of resin.Glass fibre is a kind of inorganic non-gold of excellent performance
Belong to material, good insulating, heat resistance is strong, and corrosion resistance is good, high mechanical strength, but shortcoming is that property is crisp, and wearability is poor, Neng Gouti
The tensile strength of rising mould plastics.Zinc stearate has good compatibility, can be used as releasing agent.Calcium hydroxide is as thickening
Agent, it is cheap and easy to get.Acid-base reaction generation basic salt can occur with the carboxyl of unsaturated polyester resin for calcium hydroxide.Benzoyl peroxide
Colourless to the yellowish liquid of t-butyl formate, it is not soluble in water, organic solvent can be dissolved in, in unsaturated polyester resin solidification process
Play the role of initiator.The use substitution part resin of filler, in the system of same volume, is equal to relative reduction volume receipts
Shrinkage.Meanwhile filler systems and unsaturated polyester resin System forming gap after unsaturated polyester resin curing, gap increase body
Product, relative reduction cubical contraction.
The present invention is further arranged to：According to parts by weight, 1-5 parts of UV-9 is further included.
By using above-mentioned technical proposal, UV-9, chemical name is ESCALOL 567, it is light yellow or
White crystalline powder, can effectively absorb 290-400 nanometers of ultraviolet light, hardly pick up visible ray, be had an X-rayed available for light color
Product.
The present invention is further arranged to：According to parts by weight, 0.1-0.5 parts of hexamethylphosphoramide is further included.
By using above-mentioned technical proposal, hexamethylphosphoramide is colourless or light yellow transparent liquid, be dissolved in polarity and
Nonpolar solvent, can assign product excellent outdoor anti ageing property, improve product weatherability and cold resistance.
The present invention is further arranged to：According to parts by weight, 12-18 parts of polypropylene oxide triamine is further included.
By using above-mentioned technical proposal, polypropylene oxide triamine, can be into unsaturated polyester resin as toughener
Row toughening modifying, strengthens the toughness of moulding compound.
The present invention is further arranged to：The glass fibre is alkali-free glass fibre.
By using above-mentioned technical proposal, the alkali metal oxide content in glass fibre is higher, its chemical stability,
Electrical insulation capability and intensity all can be reduced accordingly.
The present invention is further arranged to：The filler includes aluminium hydroxide and fine powder, and the aluminium hydroxide and fine powder mix
It is 1: 0.9-1 to close weight ratio.
By using above-mentioned technical proposal, aluminium hydroxide can decomposite chemical bonding water at high temperature, this reaction is suction
Thermal response, absorbs substantial amounts of latent heat, can reduce products temperature, and mutually flame, isolating oxygen can be covered with caused vaporous water
Gas, dilutes imflammable gas, so as to assign moulding compound fire resistance.
The present invention is further arranged to：The fine powder is stainless steel powder.
By using above-mentioned technical proposal, stainless steel powder has good corrosion resistance and endurance, while has excellent
Covering power, moisture can be completely cut off.
Another goal of the invention of the present invention is to provide a kind of preparation method of glass fiber reinforced unsaturated polyester plastic,
Include the following steps：
Step 1：Polystyrene and styrene are poured into container according to mixed weight ratio for 1: 1-2,1h is soaked, is stirred for disperseing
3h, stops stirring and obtains low shrinkage additive after being mutually dissolved completely；
Step 2：By weight, sequentially 55-65 parts of unsaturated polyester resin, 20-25 parts of low shrinkage additive are poured into container,
After being dispersed with stirring 10min, 0.1-0.5 parts of calcium hydroxide, 0.5-1.5 parts of peroxidized t-butyl perbenzoate, zinc stearate are added
12-18 parts of 2-5 parts, 1-5 parts of UV-9,0.1-0.5 parts of hexamethylphosphoramide and polypropylene oxide triamine stir 3min, obtain
Unsaturated polyester resin is pasted；
Step 3：The unsaturated polyester resin paste that 150-200 parts of filler is obtained with step 2 is added in being pasted toward unsaturated polyester resin
Stir 30min, then by alkali-free glass fibre 30-50 parts spill into, alkali-free glass fibre is uniformly fallen into snowflake shape, spill into the time
For 30-60s, 10min is then stirred.
By using above-mentioned technical proposal, the moulding compound of preparation has relatively low cubical contraction, good ageing resistance
Energy, excellent mechanical property.
In conclusion the invention has the advantages that：
The glass fiber reinforced unsaturated polyester plastic can reduce cubical contraction, so as to avoid because moulding compound volume is received
Contract the manufacturing deficiency brought.
Embodiment
The component table of table 1, embodiment 1-6
Note：Low shrinkage additive includes polystyrene and styrene, and filler includes aluminium hydroxide and stainless steel powder；
Unit " part " refers both to parts by weight.
Embodiment 1-5 is prepared using following preparation method：
A kind of preparation method of glass fiber reinforced unsaturated polyester plastic, includes the following steps：
Step 1：Polystyrene and styrene are poured into container, soak 1h, then 3h is dispersed with stirring on mixer, completely mutually
Stop stirring after dissolving and obtain low shrinkage additive；
Step 2：Sequentially unsaturated polyester resin, low shrinkage additive are poured into container, 10min is dispersed with stirring on mixer
Afterwards, calcium hydroxide, peroxidized t-butyl perbenzoate, zinc stearate, UV-9, hexamethylphosphoramide and polypropylene oxide are added
Triamine stirs 3min, obtains unsaturated polyester resin paste；
Step 3：Unsaturated polyester resin paste is poured into kneader, adds the unsaturated polyester resin that filler and step 2 obtain
Paste stirring 30min, then alkali-free glass fibre is spilt into, alkali-free glass fibre is uniformly fallen into snowflake shape in kneader, spill into
Time is 30-60s, then stirs 10min.
Embodiment 6 is prepared using following preparation method：
A kind of preparation method of glass fiber reinforced unsaturated polyester plastic, includes the following steps：
Step 1：Polystyrene and styrene are poured into container, soak 1h, then 3h is dispersed with stirring on mixer, completely mutually
Stop stirring after dissolving and obtain low shrinkage additive；
Step 2：Sequentially unsaturated polyester resin, low shrinkage additive are poured into container, 10min is dispersed with stirring on mixer
Afterwards, calcium hydroxide, peroxidized t-butyl perbenzoate and zinc stearate stirring 3min are added, obtains unsaturated polyester resin paste；
Step 3：Unsaturated polyester resin paste is poured into kneader, adds the unsaturated polyester resin that filler and step 2 obtain
Paste stirring 30min, then alkali-free glass fibre is spilt into, alkali-free glass fibre is uniformly fallen into snowflake shape in kneader, spill into
Time is 30-60s, then stirs 10min.
Comparative example 1
Select the embodiment 1 of the Chinese patent of Publication No. CN102504509A as a comparison case 1.
Cubical contraction is tested
Measure with buoyancy method embodiment 1-6 respectively according to GB/T 1463-2005 and comparative example 1 thicken after moulding compound and curing
The density p 1 and ρ 2 of moulding compound afterwards.
It is calculated as follows and cures cubical contraction (M)：
M=(1/ ρ 2 of 1- ρ) * 100%.
Table 2, embodiment 1-6 and comparative example 1 cure volume shrinkage test record sheet
As known from Table 2, curing cubical contraction of the invention is all higher than comparative example 1, it is seen that the present invention cure cubical contraction compared with
It is small.Embodiment 1-5 and the curing cubical contraction of embodiment 6 are close, show UV-9, hexamethylphosphoramide and polypropylene oxide
Triamine cures cubical contraction for the present invention and does not have an impact.
Mechanical property test
Embodiment 1-6 and comparative example 1 are tested according to GB/T 1447-2005, GB/T 1449-2005 and GB/T 1451-2005
Tensile strength, bending strength and impact strength.
1 mechanical property test record sheet of table 3, embodiment 1-6 and comparative example
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 | |
| Tensile strength/MPa | 177 | 183 | 185 | 180 | 175 | 171 | 167 |
| Bending strength/MPa | 261 | 257 | 267 | 259 | 263 | 249 | 238 |
| Impact strength/MPa | 178 | 184 | 187 | 182 | 175 | 154 | 134 |
As known from Table 3, tensile strength of the invention, bending strength and impact strength are all higher than comparative example 1, it is seen that the present invention has
Excellent mechanical property.And tensile strength, bending strength and the impact strength of embodiment 6 are below embodiment 1-5, it is seen that UV-
9th, the mechanical property of hexamethylphosphoramide and the polypropylene oxide triamine lifting present invention.
Anti-aging experiment
Embodiment 1-6 and comparative example 1 are surveyed according to GB/T 2573-2008 fiberglass reinforced plastics ageing properties test methods
Anti-aging property is tried, detects 5 years ages of phase.
Table 4, embodiment 1-6 and 1 anti-aging testing record sheet of comparative example (after natural climate aging)
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 | |
| Tensile strength/MPa | 171 | 177 | 183 | 174 | 170 | 161 | 148 |
| Bending strength/MPa | 254 | 252 | 264 | 253 | 258 | 237 | 216 |
| Impact strength/MPa | 173 | 179 | 185 | 176 | 170 | 143 | 112 |
Test data before using table 3 as natural climate aging.Contrast table 3 and 4 understands that tensile strength of the invention, bending are strong
Degree and the intensity of variation of impact strength are respectively less than comparative example 1, it is seen that the present invention has excellent anti-aging property.And embodiment 6
Tensile strength, the intensity of variation of bending strength and impact strength be respectively less than embodiment 1-5, it is seen that UV-9, hexamethyl phosphinylidyne three
The anti-aging property of amine and the polypropylene oxide triamine lifting present invention.
This specific embodiment is only explanation of the invention, it is not limitation of the present invention, people in the art
Member as needed can make the present embodiment the modification of no creative contribution after this specification is read, but as long as at this
All protected in the right of invention be subject to Patent Law.
Claims (8)
1. a kind of glass fiber reinforced unsaturated polyester plastic, it is characterized in that：Include the component of following parts by weight：
55-65 parts of unsaturated polyester resin
20-25 parts of low shrinkage additive
30-50 parts of glass fibre
2-5 parts of zinc stearate
0.1-0.5 parts of calcium hydroxide
0.5-1.5 parts of peroxidized t-butyl perbenzoate
150-200 parts of filler；
The low shrinkage additive includes polystyrene and styrene, and the mixed weight ratio of the polystyrene and styrene is 1:
1-2。
2. glass fiber reinforced unsaturated polyester plastic according to claim 1, it is characterized in that：According to parts by weight, go back
Including 1-5 parts of UV-9.
3. glass fiber reinforced unsaturated polyester plastic according to claim 1, it is characterized in that：According to parts by weight, go back
Including 0.1-0.5 parts of hexamethylphosphoramide.
4. glass fiber reinforced unsaturated polyester plastic according to claim 1, it is characterized in that：According to parts by weight, go back
Including 12-18 parts of polypropylene oxide triamine.
5. glass fiber reinforced unsaturated polyester plastic according to claim 1, it is characterized in that：The glass fibre is
Alkali-free glass fibre.
6. glass fiber reinforced unsaturated polyester plastic according to claim 1, it is characterized in that：The filler includes hydrogen
Aluminium oxide and fine powder, the mixed weight ratio of the aluminium hydroxide and fine powder is 1:0.9-1.
7. glass fiber reinforced unsaturated polyester plastic according to claim 6, it is characterized in that：The fine powder is stainless
Comminuted steel shot.
8. a kind of preparation method of glass fiber reinforced unsaturated polyester plastic, it is characterized in that：Include the following steps：
Step 1：According to mixed weight ratio it is 1 by polystyrene and styrene:1-2 is poured into container, is soaked 1h, is stirred for disperseing
3h, stops stirring and obtains low shrinkage additive after being mutually dissolved completely；
Step 2：By weight, sequentially 55-65 parts of unsaturated polyester resin, 20-25 parts of low shrinkage additive are poured into container,
After being dispersed with stirring 10min, 0.1-0.5 parts of calcium hydroxide, 0.5-1.5 parts of peroxidized t-butyl perbenzoate, zinc stearate are added
12-18 parts of 2-5 parts, 1-5 parts of UV-9,0.1-0.5 parts of hexamethylphosphoramide and polypropylene oxide triamine stir 3min, obtain
Unsaturated polyester resin is pasted；
Step 3：The unsaturated polyester resin paste that 150-200 parts of filler is obtained with step 2 is added in being pasted toward unsaturated polyester resin
Stir 30min, then by alkali-free glass fibre 30-50 parts spill into, alkali-free glass fibre is uniformly fallen into snowflake shape, spill into the time
For 30-60s, 10min is then stirred.
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| CN201711323768.2A CN107974063A (en) | 2017-12-12 | 2017-12-12 | Glass fiber reinforced unsaturated polyester plastic and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711323768.2A CN107974063A (en) | 2017-12-12 | 2017-12-12 | Glass fiber reinforced unsaturated polyester plastic and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115873361A (en) * | 2021-09-25 | 2023-03-31 | 宣城沣润新材料有限公司 | Low-shrinkage additive and preparation method and application thereof |
| WO2023168907A1 (en) * | 2022-03-07 | 2023-09-14 | 克瑞科技(东莞)有限公司 | Formula for anti-corrosion and anti-ultraviolet material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101016405A (en) * | 2006-02-07 | 2007-08-15 | 赵敏海 | High electric strength flame-proof continuous insulation dip molding material |
| KR20110069328A (en) * | 2009-12-17 | 2011-06-23 | 주식회사 한국몰드 | Composite material composition of low specific gravity, high strength and fast curing, and method for producing the same |
| CN102504509A (en) * | 2011-09-28 | 2012-06-20 | 上海市电力公司 | Unsaturated polyester glass fiber reinforced molding compound and application thereof |
-
2017
- 2017-12-12 CN CN201711323768.2A patent/CN107974063A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101016405A (en) * | 2006-02-07 | 2007-08-15 | 赵敏海 | High electric strength flame-proof continuous insulation dip molding material |
| KR20110069328A (en) * | 2009-12-17 | 2011-06-23 | 주식회사 한국몰드 | Composite material composition of low specific gravity, high strength and fast curing, and method for producing the same |
| CN102504509A (en) * | 2011-09-28 | 2012-06-20 | 上海市电力公司 | Unsaturated polyester glass fiber reinforced molding compound and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 陈星鹏: "不饱和聚酯树脂新型改性剂的合成及性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115873361A (en) * | 2021-09-25 | 2023-03-31 | 宣城沣润新材料有限公司 | Low-shrinkage additive and preparation method and application thereof |
| WO2023168907A1 (en) * | 2022-03-07 | 2023-09-14 | 克瑞科技(东莞)有限公司 | Formula for anti-corrosion and anti-ultraviolet material |
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Application publication date: 20180501 |