CN101215410B - Polybutylene terephthalate modified resin - Google Patents
Polybutylene terephthalate modified resin Download PDFInfo
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- CN101215410B CN101215410B CN2008100324842A CN200810032484A CN101215410B CN 101215410 B CN101215410 B CN 101215410B CN 2008100324842 A CN2008100324842 A CN 2008100324842A CN 200810032484 A CN200810032484 A CN 200810032484A CN 101215410 B CN101215410 B CN 101215410B
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- polybutylene terephthalate
- pbt
- modified resin
- elastomerics
- multipolymer
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Abstract
The invention relates to a modified resin of polybutylene terephthalate (PBT), the PBT modified resin is measured according to mass portion, which utilizes PBT whose mass portion is 92-98, modified nanometer silicon oxide whose mass portion is 2-8, and anti-oxidant whose mass portion is 0.15-0.3 to be raw materials, and the materials are mixed and welded in 210-255 DEG C, wherein, the modified nanometer silicon oxide adopts a functionalization elastic body with a functional group for PBT to toughen and modify or adopts a copolymer which is provided with a core-shell structure to coat the powder body of nanometer-grade silicon oxide. Compared with the existing PBT modified resin, the heat-proof quality, tensile strength and bending modulus of the invention are all obviously improved.
Description
Technical field
The present invention relates to a kind of polybutylene terephthalate (PBT) modified resin, specifically, relate to a kind of nano silicon (SiO that adopts the surface to handle (elastomerics coating) through " organising "
2) the PBT resin of modification.
Background technology
Polybutylene terephthalate (PBT) is a kind of thermoplastic engineering plastic, and it has advantages such as heat-resisting, resistance to chemical attack and good mechanical performance, has been widely used in fields such as electronics, electrical equipment and automobile.Along with science and technology development, to the demands for higher performance of PBT resin.Therefore, extremely chemists' concern of the modification of PBT resin.
As: WO 2004106405 provides a kind of CaCO with 5-30wt%
3The method of PBT being carried out modification with the elastomerics (ethene/butyl ester/glycidyl methacrylate) of 10-20wt%; And patent CN1563187 has reported a kind of with fiber glass reinforced PBT matrix material (wherein glass fiber content is 10-37wt%).Though to a certain extent, prior art can be improved intensity, modulus and the thermotolerance of PBT, but the defective of its existence is: the addition of additive is big (generally at 10-30wt%), and this not only makes the toughness variation of PBT, and influence its processibility, and make the glossiness variation of goods.
Polymer-modified with nanometer additive is a new technology of being paid close attention in recent years.J.Che etc. have reported and have adopted through coupling agent surface-treated nanometer SiO
2Method (Materials Letters 59 (2005) 1603-1609) by the graft polymerization modified PBT.This method steps complexity and the small molecules coupling agent of introducing can influence the weathering resistance of PBT.
Therefore, provide the simple and good PBT modified resin of over-all properties (as tensile strength, flexural strength and modulus and heat-drawn wire etc.) of a kind of preparation to become the technical issues that need to address of the present invention.
Summary of the invention
The said polybutylene terephthalate of the present invention (PBT) modified resin, according to the mass fraction (brief note: part), mainly by 92～98 parts of polybutylene terephthalates (PBT), 2～8 parts of modified manometer silicon dioxide (SiO
2) and 0.15～0.3 part of oxidation inhibitor be raw material, make through 210 ℃～255 ℃ melt blendings;
Wherein: said modified Nano SiO
2Be meant and adopt the existing multipolymer that is used for the functionalization elastomerics that has functional group of PBT toughening modifying or has nucleocapsid structure, it includes, but is not limited to: glycidyl methacrylate/vinyl cyanide copolymer, ethene/acrylic ester/glycidyl methacrylate (AX8900, AtoFina), butyl acrylate/methacrylic ester core-shell type multipolymer (EXL2330, ROHM AND HAAS) (with the butyl acrylate is nuclear, with the methacrylic ester shell) or butadiene-styrene/polymethacrylate core-shell type multipolymer (EXL2691A, ROHM AND HAAS) (with the butadiene-styrene copolymer is nuclear, with the polymethacrylate shell) the coating particle diameter is 10nm～50nm (preferred 10nm～20nm), 1.2～1.5/nm of The adsorbed hydroxyl content
2SiO
2Powder, said functionalization elastomerics or the covering amount with multipolymer of nucleocapsid structure be nano silicon weight 10%～40% (preferred covering amount is 20wt%～30wt%).
In the present invention, recommending to use relative viscosity is 0.9～1.0 (black formula viscosimetry, 25 ℃), and density is 1.2g/cm
3～1.3g/cm
3PBT; The oxidation inhibitor of recommending to use is four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010 (vapour crust (Ciba) company produces), N, [3-(3 for N '-two, the 5-di-tert-butyl-hydroxy phenyl) propionyl] (oxidation inhibitor 1098 (vapour Bagong department product) is or/and three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester [oxidation inhibitor 168 (vapour Bagong department product)] for hydrazine.
Description of drawings
Fig. 1 is the SEM figure of the PBT modified resin of embodiment 2-2 preparation.
Embodiment
A kind of method for preparing the said polybutylene terephthalate of the present invention (PBT) modified resin comprises the steps:
I. modified manometer silicon dioxide (SiO
2) preparation:
(1) multipolymer and the particle diameter that will have the functionalization elastomerics that has functional group that is used for the PBT toughening modifying respectively now or have a nucleocapsid structure is 10nm～20nm, 1.2～1.5/nm of The adsorbed hydroxyl content
2Silicon-dioxide (SiO
2) powder is scattered in the organic solvent (as tetrahydrofuran (THF) etc.), functionalization elastomerics or have the copolymer dispersion and the SiO of nucleocapsid structure
2Dispersion liquid;
(2) functionalization elastomerics or copolymer dispersion with nucleocapsid structure slowly are added to SiO
2In the dispersion liquid, stir and after 40～70 ℃ of states keep 3～7 hours, steam and remove organic solvent, the residuum drying is the SiO of modification
2Powder.
The preparation of II.PBT modified resin (target compound):
With relative viscosity is that 0.9～1.0 (black formula viscosimetry, 25 ℃), density are 1.2g/cm
3～1.3g/cm
3PBT, the modification SiO that makes by step I
2Powder and oxidation inhibitor are pressed the described mass fraction of preamble and are mixed, and place twin screw extruder, and the rotating speed of regulating twin screw extruder is 200-500rpm, under 210 ℃～255 ℃, melt extrude target compound.
The polybutylene terephthalate of gained of the present invention/elastomerics clad nano silicon dioxide composite material, nano silicon can reach about 50～100nm in the dispersion size of PBT, and its matrix material all is significantly improved than intensity, modulus and the thermotolerance of pure PBT.
Following embodiment can help further to understand the present invention, but does not limit the present invention.
Embodiment 1
I. the preparation of elastomerics clad nano SiO 2 powder:
With nano silicon (
M-5) 120 ℃ down behind the dry 4h, ultra-sonic dispersion is in tetrahydrofuran solution; With butyl acrylate/methacrylic ester core-shell type multipolymer (EXL2330, ROHM AND HAAS, consumption for by the clad nano silica weight 10%) be dissolved in (in another container) in the tetrahydrofuran solvent fully by ultrasonic.Then elastomerics-tetrahydrofuran solution slowly is added dropwise to SiO
2In-the tetrahydrofuran solution, under magnetic agitation, 60 ℃ of reaction 5h.The evaporation tetrahydrofuran solvent, drying is ground into fine powder, and is standby.
II. the preparation of target compound:
Polybutylene terephthalate (
PBT) the dry 4h under 120 ℃ of elder generation, then with the polybutylene terephthalate of 95 mass parts, the elastomerics coating modification SiO 2 powder of 5 mass parts, 0.15 the antioxidant 1010 of mass parts, 0.15 the oxidation inhibitor 168 of mass parts, add twin screw extruder, melt extrude under 210～255 ℃, rotating speed 200～500rpm, granulation is target compound.
Embodiment 2
I. the preparation of elastomerics clad nano SiO 2 powder:
With nano silicon (
M-5) 120 ℃ down behind the dry 4h, ultra-sonic dispersion is in tetrahydrofuran solution; With ethene/acrylic ester/glycidyl methacrylate elastomerics (AX8900, AtoFina) be dissolved in (in another container) in the tetrahydrofuran solvent fully by ultrasonic, the elastomerics consumption is respectively 10wt%, 20wt% and the 30wt% of nano silicon, is designated as embodiment 2-1, embodiment 2-2 and embodiment 2-3 respectively.Then elastomerics-tetrahydrofuran solution slowly is added dropwise to different SiO respectively
2In-the tetrahydrofuran solution, under magnetic agitation, 60 ℃ of reaction 5h.The evaporation tetrahydrofuran solvent, drying is ground into fine powder, and is standby.
II. the preparation of target compound:
Polybutylene terephthalate (
PBT) the dry 4h under 120 ℃ of elder generation, then with the polybutylene terephthalate of 98 mass parts, the elastomerics coating modification SiO 2 powder of 2 mass parts, 0.15 the antioxidant 1010 of mass parts, the oxidation inhibitor 168 of 0.15 mass parts adds twin screw extruder, under 210～255 ℃, rotating speed 200～500rpm, melt extrude, granulation gets three kinds of different target compounds, and wherein the SEM figure of embodiment 2-2 target compound sees Fig. 1.
Comparative Examples
Polybutylene terephthalate (
PBT), unmodified nano silicon dry 4h under 120 ℃, then with the polybutylene terephthalate of 98 mass parts, the silicon-dioxide of the unmodified processing of 2 mass parts, 0.15 the antioxidant 1010 of mass parts, 0.15 the oxidation inhibitor 168 of mass parts, add twin screw extruder, under 210～255 ℃, rotating speed 200～500rpm, melt extrude granulation.
Will be by the above-mentioned master batch of finishing at 130 ℃ of dry 4h, then that drying is good master batch is pressed standard injection moulding sample preparation in the table 1.Test result is listed in the table 1.
Table 1
By table 1 and Fig. 1 as can be known: elastomerics clad nano SiO
2Effectively improved SiO
2Dispersiveness in PBT has reached the dispersion (see figure 1) of nanoscale substantially.By modification (elastomerics coating) nanometer SiO
2, the PBT modified resin that constitutes of PBT and oxidation inhibitor, its thermotolerance, tensile strength and modulus in flexure all be significantly improved (than comparative example).
Claims (4)
1. polybutylene terephthalate modified resin, it is characterized in that, said modified resin, according to the mass fraction, main is raw material by the polybutylene terephthalate of 92～98 mass fractions, the modified manometer silicon dioxide of 2～8 mass fractions and the oxidation inhibitor of 0.15～0.3 mass fraction, makes through 210 ℃～255 ℃ melt blendings;
Wherein: said modified manometer silicon dioxide is meant and adopts the existing powder that is used for the functionalization elastomerics that has functional group of PBT toughening modifying or has the multipolymer clad nano grade silicon dioxide of nucleocapsid structure;
The said functionalization elastomerics or the covering amount of multipolymer clad nano grade silicon dioxide with nucleocapsid structure are for by 10%～40% of clad nano grade silicon dioxide weight;
Said functionalization elastomerics or the multipolymer with nucleocapsid structure are glycidyl methacrylate/vinyl cyanide copolymer, ethene/acrylic ester/glycidyl methacrylate, butyl acrylate/methacrylic ester core-shell type multipolymer or butadiene-styrene/polymethacrylate core-shell type multipolymer.
2. polybutylene terephthalate modified resin as claimed in claim 1 is characterized in that, wherein the particle diameter of the nanometer grade silica that is coated is 10nm～50nm, 1.2～1.5/nm of The adsorbed hydroxyl content
2
3. polybutylene terephthalate modified resin as claimed in claim 1 is characterized in that, wherein under 25 ℃ of conditions, the relative viscosity of said polybutylene terephthalate is 0.9～1.0, and density is 1.2g/cm
3～1.3g/cm
3
4. polybutylene terephthalate modified resin as claimed in claim 1, it is characterized in that, wherein said oxidation inhibitor is four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, N, [3-(3 for N '-two, 5-di-tert-butyl-hydroxy phenyl propionyl] hydrazine is or/and three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.
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|---|---|---|---|
| CN2008100324842A CN101215410B (en) | 2008-01-10 | 2008-01-10 | Polybutylene terephthalate modified resin |
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|---|---|---|---|
| CN2008100324842A CN101215410B (en) | 2008-01-10 | 2008-01-10 | Polybutylene terephthalate modified resin |
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| CN101215410A CN101215410A (en) | 2008-07-09 |
| CN101215410B true CN101215410B (en) | 2010-06-02 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105713358A (en) * | 2016-05-16 | 2016-06-29 | 陕西理工学院 | Preparation method of nano silicon dioxide modified PBT (polybutylene terephthalate) composite material |
| CN107096869A (en) * | 2017-06-22 | 2017-08-29 | 安徽银力铸造有限公司 | A kind of preparation method of conductive polycrystalline mullite fiber reinforced epoxy sand |
| CN110283446A (en) * | 2019-05-25 | 2019-09-27 | 招商局重工（江苏）有限公司 | The inner lining material and preparation method thereof of nonmetal flexible multiple tube |
| CN110358267B (en) * | 2019-07-31 | 2020-11-06 | 江南大学 | Anti-aging polyester composite material and preparation method thereof |
| US11952690B2 (en) | 2020-12-09 | 2024-04-09 | Taiwan Textile Research Institute | Breathable and waterproof non-woven fabric, manufacturing method of breathable and waterproof non-woven fabric, and breathable and waterproof cloth |
| CN117603565B (en) * | 2024-01-24 | 2024-04-02 | 无锡富盛阀业有限公司 | Hydrolysis-resistant polyester material, sealing gasket and application thereof in ball gasket of floating ball valve |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0834524B1 (en) * | 1995-06-19 | 2004-04-14 | Polyplastics Co. Ltd. | Polyester resin and process for the production thereof |
| WO2004106405A1 (en) * | 2003-05-28 | 2004-12-09 | Dsm Ip Assets B.V. | Polyester composition comprising polybutylene terephthalate resin |
-
2008
- 2008-01-10 CN CN2008100324842A patent/CN101215410B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0834524B1 (en) * | 1995-06-19 | 2004-04-14 | Polyplastics Co. Ltd. | Polyester resin and process for the production thereof |
| WO2004106405A1 (en) * | 2003-05-28 | 2004-12-09 | Dsm Ip Assets B.V. | Polyester composition comprising polybutylene terephthalate resin |
Non-Patent Citations (5)
| Title |
|---|
| Jianfei Che et..Graft polymerization onto nano-sized SiO2 surface and itsapplication to the modification of PBT.Materials Letters59.2005,591603-1609. * |
| 李海亮.纳米二氧化硅对PBT力学和结晶性能的影响.塑料36 1.2007,36(1),47-50. |
| 李海亮.纳米二氧化硅对PBT力学和结晶性能的影响.塑料36 1.2007,36(1),47-50. * |
| 栾宝勇等.缩聚表面接枝纳米SiO2改性PBT.合成树脂及塑料22 1.2005,22(1),44-47. |
| 栾宝勇等.缩聚表面接枝纳米SiO2改性PBT.合成树脂及塑料22 1.2005,22(1),44-47. * |
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Assignee: Shanghai Hunt Engineering Plastics Co., Ltd. Assignor: East China University of Science and Technology Contract record no.: 2012310000064 Denomination of invention: Polybutylene terephthalate modified resin Granted publication date: 20100602 License type: Exclusive License Open date: 20080709 Record date: 20120518 |
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Application publication date: 20080709 Assignee: Shanghai Hunt Engineering Plastics Co., Ltd. Assignor: East China University of Science and Technology Contract record no.: 2012310000064 Denomination of invention: Polybutylene terephthalate modified resin Granted publication date: 20100602 License type: Exclusive License Record date: 20120518 |
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