CN103740067A - Plybutylene terephthalate compound - Google Patents
Plybutylene terephthalate compound Download PDFInfo
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- CN103740067A CN103740067A CN201310751592.6A CN201310751592A CN103740067A CN 103740067 A CN103740067 A CN 103740067A CN 201310751592 A CN201310751592 A CN 201310751592A CN 103740067 A CN103740067 A CN 103740067A
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- polybutylene terephthalate
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Abstract
The invention provides a plybutylene terephthalate compound which comprises the following components in parts by weight: 100 parts of plybutylene terephthalate, 16-28 parts of main flame retardant, 3-8 parts of auxiliary flame retardant, 15-25 parts of composite additive and 20-35 parts of glass fiber. The plybutylene terephthalate compound has the advantages that an obtained plybutylene terephthalate product is good in flame retardant property.
Description
Technical field
The present invention relates to a kind of fire-retardant enhancing polybutylene terephthalate mixture, relate in particular to the polybutylene terephthalate mixture with flame retardant properties.
Background technology
Polybutylene terephthalate (below can be called for short PBT), weathering resistance, water-intake rate are low, are only 0.1%, still keep various physical property (comprising electrical property), electrical insulating property in wet environment, but volume resistance, dielectric loss are large.Heat-resisting water, bases, acids, oils but be subject to halon and corrode, hydrolytic resistance is poor, crystallization rapidly under low temperature, good forming ability.Shortcoming is that notched Izod impact strength is low, and molding shrinkage is large.Therefore most of, adopt glass fibre to strengthen or inorganic fill modification, its tensile strength, flexural strength can be enhanced about more than once, and heat-drawn wire also significantly improves.Can long term operation at 140 ℃, after glass strengthens, goods vertical, horizontal shrinking percentage is inconsistent, easily makes goods generation warpage.
Because PBT belongs to crystalline material, heat-drawn wire own is low, and notch shock susceptibility is strong, poor dimensional stability, and easy firing, shaping cycle is long, difficult processing, thereby limited its use range.PBT is carried out to extensive study on the modification both at home and abroad, be mainly the research of toughness reinforcing, enhancing, fire-retardant, blending and modifying and chemical chain extension for this reason.Most widely used is flame-retardant reinforced PBT, and it is mainly used in electronic apparatus structural part and appearance component.
Along with the rise of flame-retardant reinforced PBT demand, product how to produce excellent fire-retardancy becomes the gordian technique that producer is concerned about very much.
Summary of the invention
Technical problem to be solved by this invention is, a kind of polybutylene terephthalate mixture is provided, and can solve the bad technical problem of common polybutylene terephthalate flame retardant properties.
In order to address the above problem, the invention provides a kind of polybutylene terephthalate mixture, it is characterized in that, its parts by weight consist of: 100 parts of polybutylene terephthalates; Main flame retardant 16-28 part; Auxiliary fire retardant 3-8 part; Composite assistant 15-25 part; Glass fibre 20-35 part.
The parts by weight ratio of described main flame retardant and auxiliary fire retardant is 4:1.
The solution solvent viscosity ratio of described polybutylene terephthalate is 0.9-1.1.
Described main flame retardant is brominated epoxy resin F-2100H, dibromo neopentyl alcohol, brominated epoxy resin oligopolymer, 2, 4, 6-allyl tribromide acid phenenyl ester, polyacrylic acid pentabromo-benzyl ester, condensed bromoacenaphthylene oligopolymer, TDE, two (2, 3-dibromopropyl) fumarate, phenoxy group tetrabromobisphenol a polycarbonate oligopolymer, dibromo phenyl glycidyl ester, vinylformic acid pentabromo-benzyl ester, tribromo phenyl maleimide, Dowspray 9 oligopolymer, bromophthalic acid ester, ten tetrabromo two phenoxy groups, 1, 2-two (2, 4, 6-tribromophenoxy) ethane, tetrabromophthalic anhydride, tetrabromo-phthalate, DBS oligopolymer, two (3-bromo-2, 2-dibromo methyl-propyl) one or more in sulfite or ten dibromo two phenoxy group benzene.
Described auxiliary fire retardant is antimonous oxide.
The parts by weight of described composite assistant consist of: 100 parts of low-viscosity polybutylene terephthalates, elastomerics 15-25 part, mineral powder 10-20 part, nucleator 2-4 part, oxidation inhibitor 6-8 part.
The solution solvent viscosity ratio of described low-viscosity polybutylene terephthalate is 0.7-0.9.
Described mineral powder is selected from one or more in silicon-dioxide, magnesia crystal whisker, zeolite, three cobalt oxides, titanium dioxide, three oxidation two berylliums, zinc selenate, zinc borate, zinc phosphate, potassium felspar sand, silicon-dioxide, Study On O-cresol Epoxy Resin, ferric oxide, zinc oxide, wollastonite, zirconium silicate, talcum powder, magnesiumcarbonate, nickel oxide whisker, alumina whisker, silicon carbide whisker, GaAs whisker, mica, magnesium hydroxide, magnesiumcarbonate or talcum powder.
Described nucleator is selected from the one in long-chain linear saturated carboxylic acid sodium salt, long carbochain carboxylic acid calcium salt or two (the 4-tertiary butyl-phenylformic acid) magnesium hydroxide.
Described oxidation inhibitor is selected from Hinered phenols or amine.
The invention has the advantages that obtained polybutylene terephthalate product flame retardant properties is good, when especially the parts by weight ratio of main flame retardant and auxiliary fire retardant is 4:1, the product flame retardant properties of making according to its formula is better.
Embodiment
Below the concrete enforcement of a kind of polybutylene terephthalate mixture provided by the invention is elaborated.
embodiment 1
The present embodiment starting material and deal refer to following table, and unit is kilogram:
| Title | First group | Second group |
| Polybutylene terephthalate | 100 | 100 |
| Main flame retardant | 16 | 16 |
| Auxiliary fire retardant | 3 | 4 |
| Composite assistant | 15 | 15 |
| Glass fibre | 20 | 20 |
In the present embodiment, starting material are specially:
The solution solvent viscosity ratio of described polybutylene terephthalate is 0.9.
Described main flame retardant adopts dibromo phenyl glycidyl ester, vinylformic acid pentabromo-benzyl ester, tribromo phenyl maleimide, Dowspray 9 oligopolymer to press the mixture of the parts by weight of 2:1:2.
Described auxiliary fire retardant is antimonous oxide.
The parts by weight of described composite assistant consist of: 100 parts of low-viscosity polybutylene terephthalates, 15 parts, elastomerics, 10 parts of mineral powders, 2 parts of nucleators, 6 parts, oxidation inhibitor.Wherein the solution solvent viscosity ratio of low-viscosity polybutylene terephthalate is 0.7; Elastomerics is ionic elastomerics; Mineral powder is silicon-dioxide; Nucleator is long-chain linear saturated carboxylic acid sodium salt, and described oxidation inhibitor is tri-grades of butyl-4-methylphenols of 2,6-, is the oxidation inhibitor of Hinered phenols.
Technical process is as follows:
1, prepare composite assistant
Mineral powder is placed on to the activation treatment of carrying out in the high mixer of 110 ℃ 20 minutes;
Low-viscosity polybutylene terephthalate, elastomerics, nucleator and oxidation inhibitor are mixed, then with together with mineral powder after activation treatment, send into twin screw extruder plasticizing, mixing, obtain composite assistant.
In this step, the length-to-diameter ratio of twin screw extruder is 32:1, and main-machine screw rotating speed is at 450 revs/min, and each section of extruder temperature is controlled at 200-250 ℃, and twin screw extruder is with three cover drawing-in devices.
2, by the composite assistant obtaining in step 1 and polybutylene terephthalate, main flame retardant, auxiliary fire retardant in high-speed mixer and mixing, send into twin screw extruder plasticizing, subsequently glass fibre is fed to twin screw extruder by side feeding measurement device, mixing, obtain product.
In this step, the length-to-diameter ratio of twin screw extruder is 32:1, and main-machine screw rotating speed is at 350 revs/min, and each section of extruder temperature is controlled at 220-280 ℃.Twin screw extruder is with three cover drawing-in devices.
In the present embodiment, flame retardant resistance test result refers to following table:
| Testing method | Unit | First group | Second group |
| UL 94 | 1.0mm | V1 | V0 |
embodiment 2
The present embodiment starting material and deal refer to following table, and unit is kilogram:
| Title | First group | Second group |
| Polybutylene terephthalate | 100 | 100 |
| Main flame retardant | 28 | 28 |
| Auxiliary fire retardant | 8 | 7 |
| Composite assistant | 25 | 25 |
| Glass fibre | 35 | 35 |
In the present embodiment, starting material are specially:
The solution solvent viscosity ratio of described polybutylene terephthalate is 1.1.
Described main flame retardant adopts brominated epoxy resin F-2100H, vinylformic acid pentabromo-benzyl ester, TDE, bromophthalic acid ester to press the mixture of the parts by weight of 2:1:2.
Described auxiliary fire retardant is antimonous oxide.
The parts by weight of described composite assistant consist of: 100 parts of low-viscosity polybutylene terephthalates, 25 parts, elastomerics, 20 parts of mineral powders, 4 parts of nucleators, 8 parts, oxidation inhibitor.Wherein the solution solvent viscosity ratio of low-viscosity polybutylene terephthalate is 0.9; Elastomerics is ionic elastomerics; Mineral powder is talcum powder; Nucleator is long carbochain carboxylic acid calcium salt or two (the 4-tertiary butyl-phenylformic acid) magnesium hydroxide, and described oxidation inhibitor is pentanoic, is the oxidation inhibitor of amine.
Technical process is as follows:
1, prepare composite assistant
Mineral powder is placed on to the activation treatment of carrying out in the high mixer of 110 ℃ 20 minutes;
Low-viscosity polybutylene terephthalate, elastomerics, nucleator and oxidation inhibitor are mixed, then with together with mineral powder after activation treatment, send into twin screw extruder plasticizing, mixing, obtain composite assistant.
In this step, the length-to-diameter ratio of twin screw extruder is 32:1, and main-machine screw rotating speed is at 450 revs/min, and each section of extruder temperature is controlled at 200-250 ℃, and twin screw extruder is with three cover drawing-in devices.
2, by the composite assistant obtaining in step 1 and polybutylene terephthalate, main flame retardant, auxiliary fire retardant in high-speed mixer and mixing, send into twin screw extruder plasticizing, subsequently glass fibre is fed to twin screw extruder by side feeding measurement device, mixing, obtain product.
In this step, the length-to-diameter ratio of twin screw extruder is 32:1, and main-machine screw rotating speed is at 350 revs/min, and each section of extruder temperature is controlled at 220-280 ℃.Twin screw extruder is with three cover drawing-in devices.
In the present embodiment, flame retardant resistance test result refers to following table:
| Testing method | Unit | First group | Second group |
| UL 94 | 1.0mm | V1 | V0 |
embodiment 3
The present embodiment starting material and deal refer to following table, and unit is kilogram:
| Title | First group | Second group |
| Polybutylene terephthalate | 100 | 100 |
| Main flame retardant | 24 | 24 |
| Auxiliary fire retardant | 5 | 6 |
| Composite assistant | 18 | 18 |
| Glass fibre | 27 | 27 |
In the present embodiment, starting material are specially:
The solution solvent viscosity ratio of described polybutylene terephthalate is 1.0.
Described main flame retardant adopts condensed bromoacenaphthylene oligopolymer, tetrabromophthalic anhydride to press the mixture of the parts by weight of 3:2.
Described auxiliary fire retardant is antimonous oxide.
The parts by weight of described composite assistant consist of: 100 parts of low-viscosity polybutylene terephthalates, 20 parts, elastomerics, 15 parts of mineral powders, 3 parts of nucleators, 7 parts, oxidation inhibitor.Wherein the solution solvent viscosity ratio of low-viscosity polybutylene terephthalate is 0.8; Elastomerics is ionic elastomerics; Mineral powder is that zeolite and three cobalt oxides are by the mixture of 1:1 parts by weight; Nucleator is long carbochain carboxylic acid calcium salt or two (the 4-tertiary butyl-phenylformic acid) magnesium hydroxide, and described oxidation inhibitor is pentanoic, is the oxidation inhibitor of amine.
Technical process is as follows:
1, prepare composite assistant
Mineral powder is placed on to the activation treatment of carrying out in the high mixer of 110 ℃ 20 minutes;
Low-viscosity polybutylene terephthalate, elastomerics, nucleator and oxidation inhibitor are mixed, then with together with mineral powder after activation treatment, send into twin screw extruder plasticizing, mixing, obtain composite assistant.
In this step, the length-to-diameter ratio of twin screw extruder is 32:1, and main-machine screw rotating speed is at 450 revs/min, and each section of extruder temperature is controlled at 200-250 ℃, and twin screw extruder is with three cover drawing-in devices.
2, by the composite assistant obtaining in step 1 and polybutylene terephthalate, main flame retardant, auxiliary fire retardant in high-speed mixer and mixing, send into twin screw extruder plasticizing, subsequently glass fibre is fed to twin screw extruder by side feeding measurement device, mixing, obtain product.
In this step, the length-to-diameter ratio of twin screw extruder is 32:1, and main-machine screw rotating speed is at 350 revs/min, and each section of extruder temperature is controlled at 220-280 ℃.Twin screw extruder is with three cover drawing-in devices.
In the present embodiment, flame retardant resistance test result refers to following table:
| Testing method | Unit | First group | Second group |
| UL 94 | 1.0mm | V1 | V0 |
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a polybutylene terephthalate mixture, is characterized in that, its parts by weight consist of: 100 parts of polybutylene terephthalates; Main flame retardant 16-28 part; Auxiliary fire retardant 3-8 part; Composite assistant 15-25 part; Glass fibre 20-35 part.
2. polybutylene terephthalate mixture according to claim 1, is characterized in that, the parts by weight ratio of described main flame retardant and auxiliary fire retardant is 4:1.
3. polybutylene terephthalate mixture according to claim 1, is characterized in that, the solution solvent viscosity ratio of described polybutylene terephthalate is 0.9-1.1.
4. polybutylene terephthalate mixture according to claim 1, it is characterized in that, described main flame retardant is brominated epoxy resin F-2100H, dibromo neopentyl alcohol, brominated epoxy resin oligopolymer, 2, 4, 6-allyl tribromide acid phenenyl ester, polyacrylic acid pentabromo-benzyl ester, condensed bromoacenaphthylene oligopolymer, TDE, two (2, 3-dibromopropyl) fumarate, phenoxy group tetrabromobisphenol a polycarbonate oligopolymer, dibromo phenyl glycidyl ester, vinylformic acid pentabromo-benzyl ester, tribromo phenyl maleimide, Dowspray 9 oligopolymer, bromophthalic acid ester, ten tetrabromo two phenoxy groups, 1, 2-two (2, 4, 6-tribromophenoxy) ethane, tetrabromophthalic anhydride, tetrabromo-phthalate, DBS oligopolymer, two (3-bromo-2, 2-dibromo methyl-propyl) one or more in sulfite or ten dibromo two phenoxy group benzene.
5. polybutylene terephthalate mixture according to claim 1, is characterized in that, described auxiliary fire retardant is antimonous oxide.
6. polybutylene terephthalate mixture according to claim 1, it is characterized in that, the parts by weight of described composite assistant consist of: 100 parts of low-viscosity polybutylene terephthalates, elastomerics 15-25 part, mineral powder 10-20 part, nucleator 2-4 part, oxidation inhibitor 6-8 part.
7. polybutylene terephthalate mixture according to claim 6, is characterized in that, the solution solvent viscosity ratio of described low-viscosity polybutylene terephthalate is 0.7-0.9.
8. polybutylene terephthalate mixture according to claim 6, it is characterized in that, described mineral powder is selected from one or more in silicon-dioxide, magnesia crystal whisker, zeolite, three cobalt oxides, titanium dioxide, three oxidation two berylliums, zinc selenate, zinc borate, zinc phosphate, potassium felspar sand, silicon-dioxide, Study On O-cresol Epoxy Resin, ferric oxide, zinc oxide, wollastonite, zirconium silicate, talcum powder, magnesiumcarbonate, nickel oxide whisker, alumina whisker, silicon carbide whisker, GaAs whisker, mica, magnesium hydroxide, magnesiumcarbonate or talcum powder.
9. polybutylene terephthalate mixture according to claim 6, is characterized in that, described nucleator is selected from the one in long-chain linear saturated carboxylic acid sodium salt, long carbochain carboxylic acid calcium salt or two (the 4-tertiary butyl-phenylformic acid) magnesium hydroxide.
10. polybutylene terephthalate mixture according to claim 6, is characterized in that, described oxidation inhibitor is selected from Hinered phenols or amine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310751592.6A CN103740067A (en) | 2013-12-31 | 2013-12-31 | Plybutylene terephthalate compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310751592.6A CN103740067A (en) | 2013-12-31 | 2013-12-31 | Plybutylene terephthalate compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103740067A true CN103740067A (en) | 2014-04-23 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310751592.6A Pending CN103740067A (en) | 2013-12-31 | 2013-12-31 | Plybutylene terephthalate compound |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110240787A (en) * | 2019-05-09 | 2019-09-17 | 南通开普乐工程塑料有限公司 | Low warpage PBT composite of a kind of dimensionally stable and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH064755B2 (en) * | 1985-03-06 | 1994-01-19 | 東レ株式会社 | Flame-retardant aromatic polyester composition |
| CN101275010A (en) * | 2007-03-26 | 2008-10-01 | 上海金发科技发展有限公司 | Flame-proof reinforced Valox compound and preparation thereof |
| CN101747599A (en) * | 2008-12-16 | 2010-06-23 | 金发科技股份有限公司 | Antistatic modified polyester and method for preparing same |
| CN102040810A (en) * | 2010-12-29 | 2011-05-04 | 深圳市科聚新材料有限公司 | Polybutylece terephthalate (PBT) engineering plastics as well as preparation method and application thereof |
-
2013
- 2013-12-31 CN CN201310751592.6A patent/CN103740067A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH064755B2 (en) * | 1985-03-06 | 1994-01-19 | 東レ株式会社 | Flame-retardant aromatic polyester composition |
| CN101275010A (en) * | 2007-03-26 | 2008-10-01 | 上海金发科技发展有限公司 | Flame-proof reinforced Valox compound and preparation thereof |
| CN101747599A (en) * | 2008-12-16 | 2010-06-23 | 金发科技股份有限公司 | Antistatic modified polyester and method for preparing same |
| CN102040810A (en) * | 2010-12-29 | 2011-05-04 | 深圳市科聚新材料有限公司 | Polybutylece terephthalate (PBT) engineering plastics as well as preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110240787A (en) * | 2019-05-09 | 2019-09-17 | 南通开普乐工程塑料有限公司 | Low warpage PBT composite of a kind of dimensionally stable and preparation method thereof |
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Application publication date: 20140423 |