CN106854345A - A kind of low warpage high glaze glass fiber reinforced polybutylene terephthalate material and preparation method thereof - Google Patents
A kind of low warpage high glaze glass fiber reinforced polybutylene terephthalate material and preparation method thereof Download PDFInfo
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- CN106854345A CN106854345A CN201611175142.7A CN201611175142A CN106854345A CN 106854345 A CN106854345 A CN 106854345A CN 201611175142 A CN201611175142 A CN 201611175142A CN 106854345 A CN106854345 A CN 106854345A
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- 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
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention discloses a kind of low warpage high glaze glass fiber reinforced polybutylene terephthalate material and preparation method thereof, it is by polybutylene terephthalate (PBT)（PBT）, polyethylene terephthalate（PET）, poly butylene succinate（PBS）, flat glass fiber, toughener, ester exchange inhibitor, antioxidant, lubricant be made.First, reducing horizontal and vertical shrinkage factor difference by the PBT material of flat fiberglass reinforced；Second, the addition of PET, reduces the overall crystallinity of material, under the synergy of flat glass and PET, the low warpage properties of material are obtained；Third, because the addition of height flowing PBS resins, material overall flow mobility in injection moulding are substantially improved, increased the wetting to glass and cladding, therefore obtain high gloss.
Description
Technical field：
The present invention relates to technical field of polymer composite materials, and in particular to a kind of low warpage high glaze fiberglass reinforced gathers right
Benzene dicarboxylic acid butanediol ester material and preparation method thereof.
Background technology：
Connect very much in terms of mechanical performance and heat resistance by the polybutylene terephthalate (PBT) (PBT) of fiberglass reinforced
The material of fiberglass reinforced PA 6 is bordering on, meanwhile, the PBT of fiberglass reinforced also has that dielectric constant is high, water absorption rate is low, long compared to PA6 materials
Phase is using creep resistant is good, low cost advantage.But, because PBT crystallizing powers are strong, fiber glass reinforced PBT material is also generally deposited
The problems such as warpage, floating fibre, when being molded using the material injection, the product for obtaining is apparent coarse, and process equipment abrasion is larger.
In order to obtain the fiber glass reinforced PBT material of low warpage high gloss, conventional way is that selection glass fibre is compounded with mineral, right
PBT material is strengthened, and selects low viscosity PBT resin, increases the infiltration to glass, improves floating fibre situation, but above way is tight
The mechanical performance of PBT composite is lost again, meanwhile, the oligomer content contained in low viscous PBT resin is higher, in note
It is moulded during type and is easy to produce the defects such as gas trace and bright print.
The content of the invention
The purpose of the present invention is on the basis of the mechanical performance and heat resistance for not reducing fiber glass reinforced PBT material, there is provided
A kind of low warpage high glaze glass fiber reinforced polybutylene terephthalate material and preparation method thereof.The purpose of the present invention is led to
Cross following technical scheme realization：
A kind of low warpage high glaze glass fiber reinforced polybutylene terephthalate material, by the raw material of following weight portion
Composition：
Further scheme, the inherent viscosity of described PBT resin is between 0.68~1.1dl/g.
Further scheme, described PET resin viscosity is between 0.70~0.87dl/g.
Further scheme, described PBS resins are injection grade PBS, and number-average molecular weight is between 3000-5000.
Further scheme, described toughener is maleic anhydride grafted ethene-butylene copolymer or Glycidyl methacrylate
At least one in glyceride grafted ethene-butylene copolymer.
Further scheme, the described flat glass fiber trade mark is the flat glass of PBT resin that Japanese Japan spins product
Fine CSG 3PA-830.
Further scheme, described ester exchange inhibitor is sodium dihydrogen phosphate,Disodium dihydrogen, phosphorous acid aqueous solution or
At least one of bisphenol-A double (diphenyl phosphoesters).
Further scheme, described antioxidant is at least in Hinered phenols, thio esters, phosphite ester kind antioxidant
Kind.
Further scheme, described lubricant is Tissuemat E, stearate, ethylene bis stearamide, pentaerythrite are hard
At least one in resin acid ester.
Another goal of the invention of the invention is to provide the side of above-mentioned low warpage high glaze fiber glass reinforced PBT composite
Method, comprises the following steps：
(1) by 40-50 parts of PBT resin, 10-20 parts of EPT resins, 10-20 parts of PBS resins, 1-3 parts of toughener, 0.2-0.6
Part ester exchange inhibitor, 0.2-0.6 parts of antioxidant and 0.2-0.6 parts of lubricant mix 2- in being added to homogenizer together
5 minutes；
(2) mixed material is added in engagement type parallel equidirectional two-screw extruder by main feeding hopper, and in side
20-30 parts of flat glass fiber is added at feeding, through melting, extrusion, low warpage high glaze fiber glass reinforced PBT material is obtained；
Wherein, 230-260 DEG C of extruder barrel temperature, screw speed be 300-400r/min, vacuum be -0.04~0.1MPa.
Poly butylene succinate resin (PBS) of the present invention is injection grade aliphatic polyester, its melt temperature
About 160 DEG C, after melting, viscosity pole is dilute, can be flowed as water.It is of the present invention to be modified what is be made by flat glass
PBT material reduces horizontal and vertical shrinkage factor difference.PET of the present invention reduces the overall crystallinity of material.
Under the synergy of flat glass and PET, the low warpage properties of material are obtained；On the other hand, due to the addition of PBS resins,
Material overall flow mobility in injection moulding is substantially improved, and increased the wetting to glass and cladding, therefore obtain
High gloss.
Beneficial effects of the present invention：
1st, material preparation method of the invention is simple, workable, it is easy to large-scale industrial production, the great property of product
Valency ratio；
2nd, PET resin used in the present invention may be from discarded PET bottle, therefore recyclable substantial amounts of pet waste, section
Can environmental protection；
3rd, PBS resins used in the present invention are Biodegradable material, therefore the fiber glass reinforced PBT material is with certain
Biodegradable, belong to it is environmentally friendly；
4th, the method for improving fiber glass reinforced PBT composite of the invention does not damage its mechanical performance and its heat resistance.
Specific embodiment：
To be best understood from the present invention, with reference to embodiment, the present invention is described further.
Embodiment 1-3 is prepared according to following preparation method, the proportioning of its each component is as shown in Table 1：
(1) by 40-50 parts of PBT resin, 10-30 parts of PET resin, 10-30 parts of PBS resins, 1-3 parts of toughener, 0.2-0.6
Part ester exchange inhibitor, 0.2-0.6 parts of antioxidant and 0.2-0.6 parts of lubricant mix 2- in being added to homogenizer together
5 minutes；
(2) mixed material is added in engagement type parallel equidirectional two-screw extruder by main feeding hopper, and in side
20-30 parts of flat glass fiber is added at feeding, through melting, extrusion, low warpage high glaze fiber glass reinforced PBT material is obtained；
Wherein, 230-260 DEG C of extruder barrel temperature, screw speed be 300-400r/min, vacuum be -0.04~-0.1MPa.
Meanwhile, flat glass is replaced with into general glass fibre, and suppress without PET resin, PBS resins and ester exchange
Agent, comparative example 1-3 is prepared according to as above similar approach, and the proportioning of its each component is as shown in Table 2.
Wherein, each raw material is commercially available prod, and PBT resin inherent viscosity between 0.68~1.1dl/g；PET trees
Fat viscosity is between 0.70~0.87dl/g；PBS resins are injection grade PBS, and number-average molecular weight is between 3000-5000；Toughness reinforcing
Agent is selected from maleic anhydride grafted ethene-butylene copolymer or glycidyl methacrylate graft ethylene-butene copolymer
At least one；The flat glass fiber trade mark spins the flat glass CSG 3PA-830 of the PBT resin of product for Japanese Japan；
Ester exchange inhibitor is selected from sodium dihydrogen phosphate, disodium dihydrogen, phosphorous acid aqueous solution or bisphenol-A double (diphenyl phosphoesters)
It is at least one；Antioxidant is selected from least one in Hinered phenols, thio esters, phosphite ester kind antioxidant；Lubricant is selected from
At least one in Tissuemat E, stearate, ethylene bis stearamide, pentaerythritol stearate.
Table one：The composition of embodiment 1-3 raw materials
| Formula composition | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| PBT resin | 40 | 45 | 50 |
| PET resin | 10 | 15 | 20 |
| PBS resins | 20 | 15 | 10 |
| Flat glass | 30 | 25 | 20 |
| General glass fibre | / | / | / |
| Ester exchange inhibitor | 0.6 | 0.4 | 0.2 |
| Toughener | 1 | 2 | 3 |
| Antioxidant | 0.6 | 0.4 | 0.2 |
| Lubricant | 0.2 | 0.4 | 0.6 |
Table two：The composition of comparative example 1-3 raw materials
| Formula composition | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| PBT resin | 70 | 75 | 80 |
| PET resin | / | / | / |
| PBS resins | / | / | / |
| Flat glass | / | / | / |
| General glass fibre | 30 | 25 | 20 |
| Ester exchange inhibitor | / | / | / |
| Toughener | 1 | 2 | 3 |
| Antioxidant | 0.6 | 0.4 | 0.2 |
| Lubricant | 0.2 | 0.4 | 0.6 |
Glass prepared by low warpage high glaze fiber glass reinforced PBT composite and comparative example prepared by above-described embodiment 1~3
The density of fiber enhanced PBT material, tensile strength, bending modulus, Izod notched impact strength, glossiness, angularity, thermal deformation
Temperature etc. is detected that its examination criteria is with performance test results as shown in table three and four：
Table three：Embodiment 1-3 composite property indexs
Table four：Comparative example 1-3 composite property indexs
Note：The measuring method of angularity：It is diameter 10mm by testing sample injection moulding, thickness is the disk of 2mm, by circle
Piece one end is fixed on horizontal level (note position A), it is in alignment with A and by circular other end B apart from horizontal level
Height and be angularity.
Be can be seen that from table three and four, low warpage high glaze fiber glass reinforced PBT composite prepared by embodiment of the present invention 1-3
The fiber glass reinforced PBT material prepared with comparative example 1-3 compares, and embodiment 1-3 has glossiness and relatively low warpage higher
Spend, but mechanical performance and heat resistance are kept approximately constant.Therefore the material can meet the material of the association areas such as household electrical appliances, automobile
It is required that.
It is above-mentioned that the preferred embodiment of the present invention is described as to embodiment.The invention is not restricted to embodiment here, this
Art personnel announcement of the invention, does not depart from improvement that scope made and modification all should be in the present invention
Protection domain in.
Claims (10)
1. a kind of low warpage high glaze glass fiber reinforced polybutylene terephthalate material, it is characterised in that：By following weight
The raw material composition of part：
PBT resin 40-50 parts,
PET resin 10-20 parts,
10-20 parts of PBS resins,
Toughener 1-3 parts,
Flat glass fiber 20-30 parts,
Ester exchange inhibitor 0.2-0.6 parts,
Lubricant 0.2-0.6 parts,
Antioxidant 0.2-0.6 parts.
2. low warpage high glaze glass fiber reinforced polybutylene terephthalate material according to claim 1, its feature
It is：The inherent viscosity of described PBT resin is between 0.68 ~ 1.1dl/g.
3. low warpage high glaze glass fiber reinforced polybutylene terephthalate material according to claim 1, its feature
It is：Described PET resin viscosity is between 0.70 ~ 0.87 dl/g.
4. low warpage high glaze glass fiber reinforced polybutylene terephthalate material according to claim 1, its feature
It is：Described PBS resins are injection grade PBS, and number-average molecular weight is between 3000-5000.
5. low warpage high glaze glass fiber reinforced polybutylene terephthalate material according to claim 1, its feature
It is：Described toughener be maleic anhydride grafted ethene-butylene copolymer or glycidyl methacrylate graft ethene-
At least one in butylene copolymer.
6. low warpage high glaze glass fiber reinforced polybutylene terephthalate material according to claim 1, its feature
It is：The described flat glass fiber trade mark is that Japanese Japan spins the flat glass CSG 3PA-830 of the PBT resin of product.
7. low warpage high glaze glass fiber reinforced polybutylene terephthalate material according to claim 1, its feature
It is：Described ester exchange inhibitor is the double (hexichol of sodium dihydrogen phosphate, disodium dihydrogen, phosphorous acid aqueous solution or bisphenol-A
Base phosphate) at least one.
8. low warpage high glaze glass fiber reinforced polybutylene terephthalate material according to claim 1, its feature
It is：Described antioxidant is at least one in Hinered phenols, thio esters, phosphite ester kind antioxidant.
9. low warpage high glaze glass fiber reinforced polybutylene terephthalate material according to claim 1, its feature
It is：Described lubricant be Tissuemat E, stearate, ethylene bis stearamide, pentaerythritol stearate at least
It is a kind of.
10. a kind of low warpage high glaze fiberglass reinforced poly terephthalic acid fourth two prepared as described in claim any one of 1-9
The method of alcohol ester material, it is characterised in that：Comprise the following steps：
（1）By 40-50 parts of PBT resin, 10-20 parts of PET resin, 10-20 parts of PBS resins, 1-3 parts of toughener, 0.2-0.6 parts of ester
Exchanger inhibitor, 0.2-0.6 part antioxidant and 0.2-0.6 parts of lubricant mix 2-5 points in being added to homogenizer together
Clock；
（2）Mixed material is added in engagement type parallel equidirectional two-screw extruder by main feeding hopper, and in side feeding
Place adds 20-30 parts of flat glass fiber, through melting, extrusion, low warpage high glaze fiber glass reinforced PBT material is obtained；Wherein,
230-260 DEG C of extruder barrel temperature, screw speed are 300-400r/min, vacuum is -0.04 ~ -0.1MPa.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110093019A (en) * | 2019-05-30 | 2019-08-06 | 江阴市宏丰塑业有限公司 | A kind of fiber glass reinforced PBT/PET alloy modified material and preparation method thereof |
| CN111073226A (en) * | 2019-12-18 | 2020-04-28 | 广州市聚赛龙工程塑料股份有限公司 | High-strength high-gloss low-warpage PBT (polybutylene terephthalate) composite material as well as preparation method and application thereof |
| CN111909492A (en) * | 2020-06-29 | 2020-11-10 | 江苏金发科技新材料有限公司 | Glass fiber reinforced polybutylene terephthalate composition with low fiber floating effect |
| CN112759900A (en) * | 2020-12-28 | 2021-05-07 | 苏州旭光聚合物有限公司 | Glass fiber reinforced polybutylene terephthalate composite material and preparation method thereof |
| CN112812526A (en) * | 2021-01-26 | 2021-05-18 | 苏州塑发生物材料有限公司 | Low-warpage low-density glass fiber reinforced polylactic acid composite material and preparation method thereof |
| CN114605789A (en) * | 2022-02-28 | 2022-06-10 | 金发科技股份有限公司 | PBT composite material and preparation method and application thereof |
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| CN106519596A (en) * | 2016-09-29 | 2017-03-22 | 惠安县高智模具技术服务有限公司 | Glass fiber enhanced polybutylene terephthalate material with low warpage and high glossiness |
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| CN111073226B (en) * | 2019-12-18 | 2022-06-28 | 广州市聚赛龙工程塑料股份有限公司 | High-strength high-gloss low-warpage PBT (polybutylene terephthalate) composite material as well as preparation method and application thereof |
| CN111909492A (en) * | 2020-06-29 | 2020-11-10 | 江苏金发科技新材料有限公司 | Glass fiber reinforced polybutylene terephthalate composition with low fiber floating effect |
| CN112759900A (en) * | 2020-12-28 | 2021-05-07 | 苏州旭光聚合物有限公司 | Glass fiber reinforced polybutylene terephthalate composite material and preparation method thereof |
| CN112812526A (en) * | 2021-01-26 | 2021-05-18 | 苏州塑发生物材料有限公司 | Low-warpage low-density glass fiber reinforced polylactic acid composite material and preparation method thereof |
| CN114605789A (en) * | 2022-02-28 | 2022-06-10 | 金发科技股份有限公司 | PBT composite material and preparation method and application thereof |
| CN114605789B (en) * | 2022-02-28 | 2023-12-05 | 金发科技股份有限公司 | PBT composite material and preparation method and application thereof |
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