CN103360714A - Flame-retardant bulk molding plastic and preparation method thereof - Google Patents
Flame-retardant bulk molding plastic and preparation method thereof Download PDFInfo
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- CN103360714A CN103360714A CN2012101011201A CN201210101120A CN103360714A CN 103360714 A CN103360714 A CN 103360714A CN 2012101011201 A CN2012101011201 A CN 2012101011201A CN 201210101120 A CN201210101120 A CN 201210101120A CN 103360714 A CN103360714 A CN 103360714A
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- bulk molding
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Abstract
The invention provides flame-retardant bulk molding plastic and a preparation method thereof. The flame-retardant bulk molding plastic consists of unsaturated polyester, calcium carbonate, aluminum hydroxide, brominated polystyrene, antimonous oxide, polystyrene, glass fiber, curing agent, styrene and the like. Compared with the conventional bulk molding plastic preparation method, the preparation method disclosed by the invention comprises the following steps of: preparing the brominated polystyrene, the styrene and polystyrene into a solution; and adding other components in batch and uniformly mixing the components by a kneading machine. According to the flame-retardant bulk molding plastic and the preparation method thereof disclosed by the invention, the brominated polystyrene is uses as the flame retardant, so that V-0-level flame-retardant effect can be reached with lower adding amount. Meanwhile, the brominated polystyrene is added, so that the volume shrinkage of the bulk molding plastic can be further lowered.
Description
Technical field
The present invention relates to a kind of flame retardant type Bulk Molding Compound (BMC) and preparation method thereof.Belong to the non-metallic material technical field.
Background technology
Bulk Molding Compound (BMC).The domestic unsaturated polyester Bulk Molding Compound that often is called mainly is by GF (short glass fiber), UP (unsaturated polyester), filler, shrinking agent and the various additive material bulk prepreg through fully mixing.Because BMC has good electric property, mechanical property, thermotolerance, chemical resistance adapts to again various moulding processs, can satisfy various products to the requirement of performance, therefore more and more is subject to liking of users.Be widely used in processing electric components (insulator, ammeter box, case for circuit breaker, connection terminal, all kinds of family expenses or commercial electronic product housing), automobile component (headlight plane of reflection, back door, speaker cover etc.), stereo set housing etc.And the fire prevention in these fields is very necessary.Unsaturated polyester resin is hydrocarbon polymer, and it is the same with other most of hydrocarbon polymers, has combustibility and since BMC in to hold incendive UP as the tackiness agent of GF and filler, make it not possess flame retardant properties.In order to prepare flame retardant resistance BMC, a certain amount of flame-retardant additive that can mix in BMC is such as halogenated flame retardant, organic phosphorus flame retardant and inorganic combustion inhibitor etc.Halogenated flame retardant makes it become a most widely used based flame retardant owing to have flame retarding efficiency height, cheap advantage.But halogenated flame retardant generates more cigarette, corrosive gases and toxic gas when burning, particularly occurred in 1986 having made it face huge environmental protection pressure since Dioxins (Dioxin) problem.
Brominated Polystyrene (BPS) is as a kind of polymer halogenated flame retardant, it is a kind of in the world environmental protection fire retarding agent of approval, than traditional halogenated flame retardant, have following characteristics: (1) is owing to itself also be high molecular polymer, so they are very good with superpolymer base material consistency that will be fire-retardant, relatively can keep the original physical and mechanical properties of high polymer material; (2) because the structure of its long-chain macromolecule that has, used the fire retardant material of this based flame retardant usually can not run into the surface transport situation of fire retardant; (3) this based flame retardant is nontoxic, and its fire-retardant product can not generate many bromines hexichol to dioxin and polybrominated dibenzo-furan, and has very high thermostability, is convenient to processing and uses.
Although brominated Polystyrene has good mechanical-physical and the chemical property such as high flame retardant, thermostability and light stability, be widely used in the engineering plastics such as polybutylene terephthalate, poly terephthalic acid ethylene alcoholester, polyphenylene oxide, nylon-66.Yet seldom have before this patent report of brominated Polystyrene as the BMC fire retardant.
Summary of the invention
In view of the problem of above-mentioned existence, first purpose of the present invention provides a kind of brominated Polystyrene that adopts as the Bulk Molding Compound of fire retardant.
Second purpose of the present invention provides a kind of brominated Polystyrene that adopts as the preparation method of the Bulk Molding Compound of fire retardant.
For achieving the above object, the present invention has taked following technical scheme:
A kind of brominated Polystyrene that adopts of the present invention is as the Bulk Molding Compound of fire retardant, the prescription that it is characterized in that described flame retardant type Bulk Molding Compound, the unsaturated polyester that comprises 12～22 weight parts, the glass fibre of 10～30 weight parts, the calcium carbonate of 30～65 weight parts, the aluminium hydroxide of 10～50 weight parts, the brominated Polystyrene of 1～10 weight part, the antimonous oxide of 0～10 weight part, the polystyrene of 3～15 weight parts, the vinylbenzene of 3～15 weight parts, the organic peroxide evocating agent of 0.1～1 weight part, the vinylbenzene of 1～9 weight part.
As preferably, unsaturated polyester of the present invention is selected the unsaturated polyester that faces benzene type or metaphenylene.
As preferably, glass fibre of the present invention is selected the short glass fiber of 2.5～12mm.
As preferably, organo-peroxide of the present invention is peroxidized t-butyl perbenzoate and the peroxidation 2-ethyl tert-butyl ester.
A kind of flame retardant type Bulk Molding Compound of the present invention comprises that also auxiliary agent comprises the inner pattern releasing agent applicable of 0.5～2 weight part, the thickening material of 0.1～0.5 weight part.
As preferably, inner pattern releasing agent applicable of the present invention can be selected Zinic stearas or calcium stearate.
As preferably, thickening material of the present invention can be selected magnesium oxide or calcium oxide.
A kind of brominated Polystyrene that adopts of the present invention is as the preparation method of the Bulk Molding Compound of fire retardant, and it is characterized in that this preparation method is: each component that comprises in the Bulk Molding Compound is mixed in kneader, and it may further comprise the steps:
Step I: vinylbenzene and polystyrene, brominated Polystyrene are mixed in high-speed mixer, until the dissolving of polystyrene, brominated Polystyrene;
Step II: solution and unsaturated polyester, initiator that step I disposes are mediated 5min in kneader;
Step II I: in the mixture that Step II disposes, add aluminium hydroxide, calcium carbonate, inner pattern releasing agent applicable, thickening material, in kneader, mix 30～50min;
Step IV: glass fibre is added in the Step II I gained mixture, and mixing 3～10min can obtain Bulk Molding Compound.
Advantage of the present invention:
1, use brominated Polystyrene as fire retardant, but the flame retardant properties of Effective Raise Bulk Molding Compound.Adding a small amount of brominated Polystyrene can make the fire-retardant rank of Bulk Molding Compound reach the V-0 level.
2, use antimonous oxide as the synergistic fire retardant of brominated Polystyrene, can further improve the flame retardant properties of Bulk Molding Compound.
3, brominated Polystyrene also can reduce its volumetric shrinkage except improving the flame retardant properties of Bulk Molding Compound, thereby improves the goods apparent mass.
Specific implementation method
The invention will be further described below in conjunction with embodiment, but these embodiment have any restriction to the present invention.
Embodiment 1
Present embodiment is not for adding the sample of flame retardant brominated polystyrene and antimonous oxide.
Its prescription, preparation technology and product properties are as follows:
1,9 parts of vinylbenzene and polystyrene are mixed in high-speed mixer, prepare the Bulk Molding Compound shrinking agent.
2, the 3110 type unsaturated polyesters that 19 parts of Changzhou China day novel material company limiteds produced, shrinking agent, 0.5 part of initiator, 0.1 part of oxidation inhibitor, 0.6 part of pigment paste add in the kneader mixes 5min.
3, with 1.8 parts of Zinic stearass, 6 parts of Al (OH)
3(58 μ m), 4 parts of Al (OH)
3(38 μ m), 16 parts of CaCO
3(18 μ m), 15 parts of CaCO
3(13 μ m) adds in the kneader and mixes 45min.
4, the long glass fibre of 6mm that evenly adds 18 parts has spread in the regulation 2min, continues to stir 5min.
5, take out material, the plastics bag of packing into is tightened sack, places certain hour glass is fully infiltrated.
6, with Bulk Molding Compound compression molding in vulcanizing press of gained, be pressed into the standard code batten and be used for the flame retardant properties test.Mold pressing parameter is: 150 ℃ of molding temperatures, pressure 10MPa, fire-retardant sample clamp time 5min, Mechanics Performance Testing sample clamp time 10min.
The flame retardant properties test result is:
Fire-retardant rank: V-1 level; Oxygen index: 25.
Mechanical experimental results is:
Flexural strength: 101.6MPa, shock strength: 32.7kJ/m
2Sample volume shrinking percentage: 0.15%.
Embodiment 2
Present embodiment is the sample that adds 2 parts of flame retardant brominated polystyrenes.Compare with embodiment 1, its fire-retardant rank is increased to V-0 by V-1, and oxygen index is increased to 31 by 25, and volumetric shrinkage is down to 0.12% by 0.15%, and flexural strength and shock strength do not have considerable change.Experiment shows that a small amount of brominated Polystyrene can improve the flame retardant properties of sample, reduces volumetric shrinkage, and less to Effect on Mechanical Properties.
Its prescription, preparation technology and product properties are as follows:
1,9 parts of vinylbenzene and polystyrene, 2 parts of brominated Polystyrenes are mixed in high-speed mixer, prepare the Bulk Molding Compound shrinking agent.
2, will mix 5min in 3110 type unsaturated polyesters of 19 parts of Changzhou China day novel material company limited product, the shrinking agent that comprises brominated Polystyrene, 0.5 part of initiator, 0.1 part of oxidation inhibitor, 0.6 part of pigment paste adding kneader.
3, with 1.8 parts of Zinic stearass, 6 parts of Al (OH)
3(58 μ m), 4 parts of Al (OH)
3(38 μ m), 14 parts of CaCO
3(18 μ m), 15 parts of CaCO
3(13 μ m) adds in the kneader and mixes 45min.
4, the long glass fibre of 6mm that evenly adds 18 parts has spread in the regulation 2min, continues to stir 5min.
5, take out material, the plastics bag of packing into is tightened sack, places certain hour glass is fully infiltrated.
6, with Bulk Molding Compound compression molding in vulcanizing press of gained, be pressed into the standard code batten and be used for the flame retardant properties test.Mold pressing parameter is: 150 ℃ of molding temperatures, pressure 10MPa, fire-retardant sample clamp time 5min, Mechanics Performance Testing sample clamp time 10min.
The flame retardant properties test result is:
Fire-retardant rank: V-0 level; Oxygen index: 31.
Mechanical experimental results is:
Flexural strength: 99.7MPa, shock strength: 34kJ/m
2Sample volume shrinking percentage: 0.12%.
Embodiment 3
Present embodiment is the sample that adds 2 parts of brominated Polystyrenes, 2 parts of antimonous oxides.Compare with embodiment 1, its fire-retardant rank is increased to V-0 by V-1, and oxygen index is increased to 34 by 25, and volumetric shrinkage is down to 0.10% by 0.15%, and flexural strength and shock strength slightly are improved.Experiment shows that a small amount of brominated Polystyrene and antimonous oxide can improve the flame retardant properties of sample, reduces volumetric shrinkage, and less to Effect on Mechanical Properties.Present embodiment is compared with embodiment 2, and flame retardant properties further improves, and shows that brominated Polystyrene and antimonous oxide have the cooperative flame retardant effect.
Its prescription, preparation technology and product properties are as follows:
1,9 parts of vinylbenzene and polystyrene, 2 parts of brominated Polystyrenes are mixed in high-speed mixer, prepare the Bulk Molding Compound shrinking agent.
2, will mix 5min in 3110 type unsaturated polyesters of 19 parts of Changzhou China day novel material company limited product, the shrinking agent that comprises brominated Polystyrene, 0.5 part of initiator, 0.1 part of oxidation inhibitor, 0.6 part of pigment paste adding kneader.
3, with 1.8 parts of Zinic stearass, 4 parts of Al (OH)
3(58 μ m), 6 parts of Al (OH)
3(38 μ m), 12 parts of CaCO
3(18 μ m), 15 parts of CaCO
3(13 μ m), 2 parts of antimonous oxides add in the kneader and mix 45min.
4, the long glass fibre of 6mm that evenly adds 18 parts has spread in the regulation 2min, continues to stir 5min.
5, take out material, the plastics bag of packing into is tightened sack, places certain hour glass is fully infiltrated.
6, with Bulk Molding Compound compression molding in vulcanizing press of gained, be pressed into the standard code batten and be used for the flame retardant properties test.Mold pressing parameter is: 150 ℃ of molding temperatures, pressure 10MPa, fire-retardant sample clamp time 5min, Mechanics Performance Testing sample clamp time 10min.
The flame retardant properties test result is:
Fire-retardant rank: V-0 level; Oxygen index: 34.
Mechanical experimental results is:
Flexural strength: 96.3MPa, shock strength: 31.1kJ/m
2Sample volume shrinking percentage: 0.10%.
Embodiment 4
Present embodiment is the sample that adds 1 part of brominated Polystyrene, 1 part of antimonous oxide.Compare with embodiment 1, its fire-retardant rank is increased to V-0 by V-1, and oxygen index is increased to 33 by 25, and volumetric shrinkage is down to 0.12% by 0.15%, and flexural strength and shock strength slightly descend.Experiment shows that a small amount of brominated Polystyrene and antimonous oxide can improve the flame retardant properties of sample, the reduction volumetric shrinkage, and mechanical property had to a certain degree improvement.
Its prescription, preparation technology and product properties are as follows:
1,9 parts of vinylbenzene and polystyrene, 1 part of brominated Polystyrene are mixed in high-speed mixer, prepare the Bulk Molding Compound shrinking agent.
2, will mix 5min in 3110 type unsaturated polyesters of 19 parts of Changzhou China day novel material company limited product, the shrinking agent that comprises brominated Polystyrene, 0.5 part of initiator, 0.1 part of oxidation inhibitor, 0.6 part of pigment paste adding kneader.
3, with 1.8 parts of Zinic stearass, 4 parts of Al (OH)
3(58 μ m), 6 parts of Al (OH)
3(38 μ m), 14 parts of CaCO
3(18 μ m), 15 parts of CaCO
3(13 μ m), 1 part of antimonous oxide add in the kneader and mix 45min.
4, the long glass fibre of 6mm that evenly adds 18 parts has spread in the regulation 2min, continues to stir 5min.
5, take out material, the plastics bag of packing into is tightened sack, places certain hour glass is fully infiltrated.
6, with Bulk Molding Compound compression molding in vulcanizing press of gained, be pressed into the standard code batten and be used for the flame retardant properties test.Mold pressing parameter is: 150 ℃ of molding temperatures, pressure 10MPa, fire-retardant sample clamp time 5min, Mechanics Performance Testing sample clamp time 10min.
The flame retardant properties test result is:
Fire-retardant rank: V-0 level; Oxygen index: 32.
Mechanical experimental results is:
Flexural strength: 103.3MPa, shock strength: 33.6kJ/m
2Sample volume shrinking percentage: 0.12%.
Claims (8)
1. one kind is adopted brominated Polystyrene as the Bulk Molding Compound of fire retardant, the prescription that it is characterized in that described flame retardant type Bulk Molding Compound, the unsaturated polyester that comprises 12～22 weight parts, the glass fibre of 10～30 weight parts, the calcium carbonate of 30～65 weight parts, the aluminium hydroxide of 10～50 weight parts, the brominated Polystyrene of 1～10 weight part, the antimonous oxide of 0～10 weight part, the polystyrene of 3～15 weight parts, the vinylbenzene of 3～15 weight parts, the organic peroxide evocating agent of 0.1～1 weight part, the vinylbenzene of 1～9 weight part.
2. a kind of brominated Polystyrene that adopts according to claim 1 is as the Bulk Molding Compound of fire retardant, it is characterized in that described unsaturated polyester selects the unsaturated polyester that faces benzene type or metaphenylene.
3. a kind of brominated Polystyrene that adopts according to claim 1 is as the Bulk Molding Compound of fire retardant, it is characterized in that described glass fibre selects the short glass fiber of 2.5～12mm.
4. a kind of brominated Polystyrene that adopts according to claim 1 is characterized in that as the Bulk Molding Compound of fire retardant described organo-peroxide is peroxidized t-butyl perbenzoate and the peroxidation 2-ethyl tert-butyl ester.
5. a kind of brominated Polystyrene that adopts according to claim 1 is as the Bulk Molding Compound of fire retardant, the prescription that it is characterized in that described flame retardant type Bulk Molding Compound, comprise that also auxiliary agent comprises the inner pattern releasing agent applicable of 0.5～2 weight part, the thickening material of 0.1～0.5 weight part.
6. a kind of brominated Polystyrene that adopts according to claim 5 is as the Bulk Molding Compound of fire retardant, it is characterized in that described inner pattern releasing agent applicable can select Zinic stearas or calcium stearate.
7. a kind of brominated Polystyrene that adopts according to claim 5 is as the Bulk Molding Compound of fire retardant, it is characterized in that described thickening material can select magnesium oxide or calcium oxide.
8. one kind is adopted brominated Polystyrene as Bulk Molding Compound of fire retardant and preparation method thereof, and it is characterized in that this preparation method is: each component that comprises in the Bulk Molding Compound is mixed in kneader, and it may further comprise the steps:
Step I: vinylbenzene and polystyrene, brominated Polystyrene are mixed in high-speed mixer, until the dissolving of polystyrene, brominated Polystyrene;
Step II: solution and unsaturated polyester, initiator that step I disposes are mediated 5min in kneader;
Step II I: in the mixture that Step II disposes, add aluminium hydroxide, calcium carbonate, inner pattern releasing agent applicable, thickening material, in kneader, mix 30～50min;
Step IV: glass fibre is added in the Step II I gained mixture, and mixing 3～10min can obtain Bulk Molding Compound.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105365148A (en) * | 2014-08-26 | 2016-03-02 | 刘平 | Manufacturing process of car lamp reflector |
| CN108084681A (en) * | 2017-12-29 | 2018-05-29 | 宁波市镇海科比特音响有限公司 | A kind of casing of loudspeaker box composite material and preparation method thereof |
| CN112356377A (en) * | 2020-11-02 | 2021-02-12 | 庆云茂盛源复合材料有限公司 | Production process of excrement leaking plate |
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| CN1966567A (en) * | 2006-11-24 | 2007-05-23 | 北京理工大学 | Flame-proof polystyrene composition and its preparation method |
| CN101265357A (en) * | 2008-04-30 | 2008-09-17 | 宁波华缘玻璃钢电器制造有限公司 | Self-lubricating wear-resisting agglomerate moulding material |
| CN101709141A (en) * | 2009-11-24 | 2010-05-19 | 河南省电力公司南阳供电公司 | Formula and preparation method of unsaturated polyester resin bulk molding compound (BMC) |
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2012
- 2012-04-01 CN CN201210101120.1A patent/CN103360714B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966567A (en) * | 2006-11-24 | 2007-05-23 | 北京理工大学 | Flame-proof polystyrene composition and its preparation method |
| CN101265357A (en) * | 2008-04-30 | 2008-09-17 | 宁波华缘玻璃钢电器制造有限公司 | Self-lubricating wear-resisting agglomerate moulding material |
| CN101709141A (en) * | 2009-11-24 | 2010-05-19 | 河南省电力公司南阳供电公司 | Formula and preparation method of unsaturated polyester resin bulk molding compound (BMC) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105365148A (en) * | 2014-08-26 | 2016-03-02 | 刘平 | Manufacturing process of car lamp reflector |
| CN108084681A (en) * | 2017-12-29 | 2018-05-29 | 宁波市镇海科比特音响有限公司 | A kind of casing of loudspeaker box composite material and preparation method thereof |
| CN112356377A (en) * | 2020-11-02 | 2021-02-12 | 庆云茂盛源复合材料有限公司 | Production process of excrement leaking plate |
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| CN103360714B (en) | 2016-12-14 |
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