CN1167784A - Polyester elastomer and multifunction group epoxy modified polyester composition and process for preparing same - Google Patents
Polyester elastomer and multifunction group epoxy modified polyester composition and process for preparing same Download PDFInfo
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- CN1167784A CN1167784A CN 96109103 CN96109103A CN1167784A CN 1167784 A CN1167784 A CN 1167784A CN 96109103 CN96109103 CN 96109103 CN 96109103 A CN96109103 A CN 96109103A CN 1167784 A CN1167784 A CN 1167784A
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- polyester elastomer
- polymer blend
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Abstract
A polyester composition modified by polyester elastomer and multi-function-group epoxy resin contains PET resin, polyester elastomer that is straight-chain or branched polyester-polyether polyblock copolymer, epoxy resin with 2-4 functional groups, monometal salt of terephthalic acid as nucleator, and glass fibre. Said composition features low preparing temp (220-270 deg. C), good flowability of its melt, smooth and bright surface and high impact strength.
Description
The present invention relates to a kind of main chain and contain the aromatic polyester composition of carboxylic acid ester groups, particularly a kind of polyethylene terephthalate (PET) and polyester elastomer, and the composition and method of making the same of micro-polyfunctional epoxy resin.
Polyester (PET) has excellent property, and is cheap, and the characteristics of sufficient raw are widely used in and make fiber, film and engineering plastics.But the PET of non-modified, processing temperature is everlasting more than 290-300 ℃.In the screw rod extrusion process, molecular weight is easily degraded, and causes erosion-resisting characteristics low simultaneously.The PET crystallization velocity of non-modified is also slow, needs to add crystallization nucleating agent, to improve the crystallization rate of PET, can be used for moulded parts.The clear 64-07557 of JP-discloses a kind of polyester (PET) composition with polyester elastomer and polyfunctional epoxy resin modification, the processing temperature of said composition is 280-300 ℃, the flat 7-278416 of JP-discloses a kind of polymer blend, polyester elastomer is that the polyester of content 33.3% and the segmented copolymer of bisphenol A modified poly-epoxy hexane ether carry out modification and polyfunctional epoxy resin and Sodium Benzoate nucleator content height in the said composition, thereby has influenced the processing characteristics of said composition.
It is 280-300 ℃ that the present invention has overcome polyester in the prior art (PET) processing temperature, and polyester elastomer and the higher deficiency of nucleator content, and provide the PET resin of a kind of available regular grade [η]=0.65, and can process stable PET composition at the course of processing good fluidity of processing below 270 ℃.
Composition of the present invention contains following component and content (weight percentage):
PET resin content 57-97 (%)
[η]＝0.65
Polyester elastomer 1-10 (%)
Polyfunctional epoxy resin 0.1-1.2 (%)
Nucleator 0.1-0.6 (%)
Glass fibre 30-40%
Oxidation inhibitor 0.2-0.3%
The intrinsic viscosity of above-mentioned PET resin [η]=0.65
Above-mentioned polyester elastomer is straight chain type or ramiform polyester-polyether multi-block copolymer, has following general formula:
R-CH
2-CH
2-；
Wherein n=2, or 4-CH
2-CH
2-CH
2-CH-
The hard segment of above-mentioned polyester elastomer can be polyethylene terephthalate (n=2); It also can be polybutylene terephthalate (n=4); Soft chain segment can be a polytetramethylene ether, polyethylene oxide, poly(propylene oxide), or the copolyether of poly(propylene oxide) and polytetramethylene ether.As polyethylene terephthalate-polytetramethylene ether (PET-PTMG) polyester elastomer, polyethylene terephthalate-poly-(tetramethylene ether-propylene oxide) copolyether polyester elastomer (PET-PTMG-PPG) or polyethylene terephthalate-polyethylene oxide ether polyester elastomer (PET-PEG), polybutylene terephthalate-polytetramethylene ether polyester elastomer, polybutylene terephthalate-poly(propylene oxide) ether polyester elastomer or polybutylene terephthalate-polyethylene oxide polyester elastomer.
Described polyfunctional epoxy resin is two functional groups, trifunctional or four-functional group epoxy compounds or novolac epoxy.
Have above-mentioned hard section polyester-polyethers multiblock and add the branch agent in preparation process with soft segment structure, just can obtain corresponding three branches and four branch polyester elastomers, they are better to the toughening effect of PET than straight chain type polyester elastomer, can obtain higher shock resistance.
Soft segment content=40-80 (%), soft chain segment molecular weight=1000-6000
Polyester elastomer role in the present invention has 3 points.(1) processing fluidity of improvement PET, the processing temperature of reduction PET.(2) promote the PET crystallization.(3) PET there is certain toughening effect.
Polyester elastomer sees Table 1 to the flowability of PET:
Table 1, elastomerics improve the PET flowability
Elastomerics (%) PET flow (Grams Per Minute)
0 27.0
5 36.1
10 40.1
The used nucleator of the present invention is the efficient nucleator of " non-chemical nucleation type " small molecules organic carboxyl acid salt, has following general formula:
Me=Na, K or Zn in the formula; R=CH
3, C
2H
5Or C
3H
7Polyester elastomer sees Table 2 to the crystalline influence of PET:
Table 2,
Sample t1/2 (second)
(Tc＝200℃)
PET 65.16
PET+5％PET-(PTMG-PPG) 24.1
PET+5％PET-PTMG 2.2
PET+5％PET-(PTMG-PPG)
+ 0.3% nucleator 9.05 of the present invention
PET+5％PET-PTMG+
0.3% nucleator 7.36 of the present invention
Described polyfunctional compound mainly is meant micromolecular trifunctional or four-functional group epoxy compounds and macromolecular novolac epoxy resin.In order to regulate functional group densities and to be convenient to be processed as purpose, also can be with novolac epoxy resin and two functional group epoxy resins and usefulness, representational trifunctional epoxy compounds has: 4.5 epoxy cyclohexanes 1,2-dioctyl phthalate 2-glycidyl ester (TDE
85), 1,1-two (methoxyl group)-3.4 epoxy cyclohexane diglycidylether, 4-(N, N '-2-glycidyl amino) phenol glycidyl ether, the four-functional group epoxy compounds has: two Resorcinol formal four glycidyl ethers (F-76) polyfunctional epoxy resin is a novolac epoxy.Be used for and two functional group's epoxy compoundss of usefulness have the tetrahydrophthalic acid 2-glycidyl ester, its effect is in the course of processing and the terminal carboxylic acid group's effect of PET, generate starlike or pectination macromolecular structure, the PET molecular weight is increased, shock resistance is improved, trifunctional and four-functional group epoxy and PET react in the course of processing, make PET form three arms or four arm star topologies respectively; Novolac epoxy resin then reacts with PET, makes PET form pectination, and its main effect is that the erosion-resisting characteristics of PET composition is increased.
Add the attached fat of different structure multifunction group epoxy, the data that PET composition erosion-resisting characteristics increases are listed in table 3.
Table 3, polyfunctional epoxy resin are to improvement PET raw material [η] the multifunction group epoxy % shock strength Kg.cm/cm of erosion-resisting characteristics
2Regular grade 0.65 0 3.50 tackify level 0.85 0 5.31 regular grade 0.65 trifunctional 0.6 7.38 regular grade 0.65 four-functional group 0.6 4.25 regular grade 0.65 phenolic aldehyde epoxy 4.88 can see that by table 3 PET of regular grade [η]=0.65 does not add the polyfunctional group epoxy, shock strength is low, add multifunction group epoxy, erosion-resisting characteristics increases substantially.
Table 4, different structure multi-group epoxy compound count content (%) breach resistance to impact shock to the improvement epoxy compounds functional group of PET shock resistance
Kg.cm/cm
2Do not add/0 3.50 phenolic aldehyde epoxy polyfunctional groups, 0.6 4.88TDE
85Trifunctional 0.6 7.38F-76 functional group 0.6 4
Table 5, multi-group epoxy compound are to toughness reinforcing effect PET raw material [η] the epoxy compounds % resistance to impact shock kg./cm of PET
20.65 0 4.000.85,0 5.310.65 0.6 6.81
In actual applications, above polyfunctional epoxy resin can be used alone or as a mixture.
Table 6, different content polyester elastomer (PET-PTMG) influence polyester elastomer content (%) breach resistance to impact shock kg.cm/cm
2
0 4.95
3 5.63
5 6.38
The toughening effect structure type breach resistance to impact shock kg.cm/cm of table 7, different structure polyester elastomer
2
PET-PTMG PET-PEG PET (PTMG-PPG) straight chain type 3.42 2.85/four branches 4.00 3.12/three branches 5.59 4.91 4.87
The used nucleator of the present invention do not make the PET molecular weight degradation, and consumption is few at processing temperature 260-270 ℃ of the PET composition, the efficient height, be used with the 1-10% polyester elastomer, crystallization rate is further accelerated, polyester elastomer is again the crystallization promoter of PET in prescription.
A kind of preparation method with polyester elastomer and multifunction group epoxy modified polymer blend of the present invention is that step is carried out in the following order:
Various raw materials are pressed following component and content (weight percentage):
PET resin content 57-97%
[η]＝0.65
Polyester elastomer 1-10%
Polyfunctional epoxy resin 0.1-1.2%
Nucleator 0.1-0.6%
Glass fibre 0-50%
Oxidation inhibitor 0.2-0.3% joins in the forcing machine, melt extrudes at 220-270 ℃, and granulation is made with poly-elastomerics and multifunction group epoxy modified polymer blend.
Modified poly ester composition processing temperature of the present invention is lower than 270 ℃, and it is good to have a fluidity of molten, and crystallization velocity is fast, and the moulded work surface-brightening has high resistance to impact shock, is easy to suitability for industrialized production.
Embodiment 1,
With [η]=0.65PET resin and 5% polyester elastomer (PET-PTMG), 0.3% nucleator terephthalic acid list sodium salt, 0.5% novolac epoxy and oxidation inhibitor 711 (1: 1) mixture, 0.2% antioxidant 1010,30% glass (chemical industry-type) is 100-110 ℃ of vacuum-drying after 10 hours, by the screw rod blend, extruder temperature 220-270 ℃, obtain uniform blend.Embodiment 2,
With [η]=0.65 PET resin and 0.3% nucleator, 0.2% antioxidant 1010,5% polyester elastomer (PET-PTMG) and 0.5% various structure ring oxygen compounds, by the screw rod blend, processing temperature 220-270 ℃.Comparative example 1,
The present invention adopts with regular grade PET[η]=0.65 be raw material, by adding a small amount of multi-group epoxy compound, making shock resistance is that raw material is taller than with high viscosity ([η]=0.85) PET.
Respectively with the PET and 0.3% nucleator of [η]=0.65 and [η]=0.85,0.2% antioxidant 1010, (PET-PTMG) does not add or adds novolac epoxy 0.6% to 5% polyester elastomer, carries out the screw rod blend at 220-270 ℃.Embodiment 3,
With [η]=0.65 PET, 0.3% nucleator, 0.6%, 0.2% antioxidant 1010 and different content polyester elastomer (PET-PTMG) carry out the screw rod blend at 220-270 ℃.Embodiment 4,
With [η]=0.65 PET, 0.3% nucleator, 0.6% polyfunctional epoxy resin, 0.2% antioxidant 1010, respectively with the polyester elastomer (PET-PTMG) of various structures, PET-PEG and PET (PTMG-PPG), by the screw rod blend, Heating temperature 220-270 ℃.Comparative example 2
With [η]=0.65 PET and different sorts elastomerics with embodiment 4, carry out the screw rod blend under the same terms, even SBS content height to 10% is that 5% shock resistance is good not as good as polyester elastomer still.
PET resistance to impact shock elastomer content (%) breach resistance to impact shock kg.cm/cm
2Polyester elastomer (PET-PTMG) 5 6.19SBS (B content 70%) 5 4.81SBS (B content 70%) 10 5.00 embodiment 5,
With PET[η]=0.65 with 0-0.5% nucleator 0-10% polyester elastomer, 0.2% antioxidant 1010 is by the screw rod blend, Heating temperature is 220-270 ℃, measure the crystal property of product, can see polyester elastomer also has the crystallization promoter action, and then crystallization is faster to add nucleator.
PET crystallinity (Tc=200 ℃) nucleator (%) polyester elastomer (%) induced crystallization time (second) hypocrystalline time T
1/2(second) 00 18.6 72.00.5 0 5.0 9.60.5 10 4.2 7.8
Claims (14)
1, a kind of polymer blend of modification comprises the PET resin, and polyfunctional epoxy resin and glass fibre is characterized in that also comprising polyester elastomer and nucleator, and its composition and content amount (weight percentage) are as follows:
PET resin content 57-97 (%)
[η]＝0.65
Polyester elastomer 1-10 (%)
Polyfunctional epoxy resin 0.1-1.2 (%)
Nucleator 0.1-0.6 (%)
Glass fibre 0-50%
Oxidation inhibitor 0.2-0.3%
The intrinsic viscosity of above-mentioned PET resin [η]=0.65
Above-mentioned polyester elastomer is linearity or branching polyterephthalate one poly alkyl ether segmented copolymer, has following general formula:
R-CH
2-CH
2-；
Wherein n=2 or 4-CH
2-CH
2-CH
2-CH-
Soft segment content=60～80 (%), soft chain segment molecular weight=1000-6000
Described nucleator is a terephthalate monocarboxylic acid metal-salt, and its general formula is:
R is CH in the formula
3, C
2H
5, C
3H
7M is Na, K, Mg, Zn
2, the polymer blend of a kind of modification according to claim 1 is characterized in that described nucleator is a terephthalate monocarboxylic acid sodium salt.
3, the polymer blend of a kind of modification according to claim 1 is characterized in that described linear polyester elastomerics is polyethylene terephthalate-polytetramethylene ether polyester elastomer, polyethylene terephthalate-(tetramethylene ether-propylene oxide) copolyether polyester elastomer or polyethylene terephthalate-polyethylene oxide ether polyester elastomer.
4, the polymer blend of a kind of modification according to claim 1 is characterized in that described linear polyester elastomerics is polybutylene terephthalate-polytetramethylene ether polyester elastomer, polybutylene terephthalate-(tetramethylene ether-propylene oxide) copolyether polyester elastomer or polybutylene terephthalate-polyethylene oxide polyester elastomer.
5, the polymer blend of a kind of modification according to claim 1 is characterized in that described branched polyester elastomerics is three branch polyester elastomers of aforesaid right requirement 3 or 4 described various structure polyester elastomers.
6, the polymer blend of a kind of modification according to claim 1 is characterized in that described branched polyester elastomerics is four branch polyester elastomers of aforesaid right requirement 3 or 4 described various structure polyester elastomers.
7, the polymer blend of a kind of modification according to claim 1 is characterized in that described polyfunctional epoxy resin is two functional groups, trifunctional or four-functional group epoxy compounds or novolac epoxy.
8, the polymer blend of a kind of modification according to claim 7, it is characterized in that described trifunctional epoxy compounds is 4,5 epoxy cyclohexanes 1,2-dioctyl phthalate 2-glycidyl ester, 1,1-two (methoxyl group)-3,4 epoxy cyclohexane diglycidylethers, or 4-(N, N '-2-glycidyl amino) phenol glycidyl ether.
9, the polymer blend of a kind of modification according to claim 7 is characterized in that described four-functional group epoxy compounds is two Resorcinol formal four glycidyl ethers.
10, the polymer blend of a kind of modification according to claim 7 is characterized in that described epoxy compounds is the tetrahydrophthalic acid 2-glycidyl ester.
11, the preparation method of the polymer blend of a kind of modification according to claim 1 is characterized in that step is carried out in the following order:
Various raw materials are pressed following component and content (weight percentage):
PET resin content 57-97 (%)
[η]＝0.65
Polyester elastomer 1-10 (%)
Polyfunctional epoxy resin 0.1-1.2 (%)
Nucleator 0.1-0.6 (%)
Glass fibre 0-50%
Oxidation inhibitor 0.2-0.3% joins in the forcing machine, melt extrudes at 260-270 ℃, and granulation is made with polyester elastomer and multifunction group epoxy modified polymer blend.
12, the preparation method of the polymer blend of a kind of modification according to claim 11 is characterized in that described nucleator is a terephthalate monocarboxylic acid sodium salt.
13, the preparation method of the polymer blend of a kind of modification according to claim 11 is characterized in that described polyester elastomer is linearity or branching polyterephthalate one poly alkyl ether segmented copolymer.
14, the preparation method of the polymer blend of a kind of modification according to claim 10 is characterized in that described polyfunctional epoxy resin is two functional groups, trifunctional or four-functional group epoxy compounds or novolac epoxy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109103A CN1079411C (en) | 1996-07-19 | 1996-07-19 | Polyester elastomer and multifunction group epoxy modified polyester composition and process for preparing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109103A CN1079411C (en) | 1996-07-19 | 1996-07-19 | Polyester elastomer and multifunction group epoxy modified polyester composition and process for preparing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1167784A true CN1167784A (en) | 1997-12-17 |
| CN1079411C CN1079411C (en) | 2002-02-20 |
Family
ID=5120225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96109103A Expired - Fee Related CN1079411C (en) | 1996-07-19 | 1996-07-19 | Polyester elastomer and multifunction group epoxy modified polyester composition and process for preparing same |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070421B (en) * | 2006-12-22 | 2010-09-08 | 深圳市科聚新材料有限公司 | High-heat-resisting glass-fiber reinforced polyester composite material and preparing method |
| CN102786676A (en) * | 2012-08-10 | 2012-11-21 | 金发科技股份有限公司 | Polyester elastomer with branching structure and preparation method thereof |
| CN105324434A (en) * | 2013-07-01 | 2016-02-10 | 株式会社钟化 | High thermal conductivity thermoplastic resin composition with excellent injection moldability |
| CN105754079A (en) * | 2014-11-10 | 2016-07-13 | 财团法人工业技术研究院 | Thermoplastic polyester elastomer and method for forming same |
| CN110444664A (en) * | 2019-08-13 | 2019-11-12 | 昆山维信诺科技有限公司 | A kind of flexible substrate, display panel and its display device |
| CN111073231A (en) * | 2019-12-31 | 2020-04-28 | 聚威工程塑料(上海)有限公司 | PET material with ultrahigh elongation at break and preparation method thereof |
| CN115011081A (en) * | 2022-06-10 | 2022-09-06 | 中广核俊尔(浙江)新材料有限公司 | Glass fiber reinforced PET composition with rapid crystallization and preparation method thereof |
Families Citing this family (1)
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| TWI735323B (en) | 2020-08-31 | 2021-08-01 | 南亞塑膠工業股份有限公司 | Modified thermoplastic polyester elastomer, and waterproof and breathable membrane |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59168055A (en) * | 1983-03-14 | 1984-09-21 | Toyobo Co Ltd | Polyester block copolymer composition |
| GB2146648B (en) * | 1983-09-16 | 1986-12-10 | Bip Chemicals Ltd | Polyethylene terephthalate moulding compositions |
| JPS63238154A (en) * | 1987-03-26 | 1988-10-04 | Mitsubishi Rayon Co Ltd | Polyethylene terephthalate resin composition |
| JP3547230B2 (en) * | 1995-09-05 | 2004-07-28 | 東レ・デュポン株式会社 | Elastic knitted fabric that changes color according to elongation and method of manufacturing the same |
| JPH1075557A (en) * | 1996-08-29 | 1998-03-17 | Secoh Giken Inc | Electromagnetic plunger |
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1996
- 1996-07-19 CN CN96109103A patent/CN1079411C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070421B (en) * | 2006-12-22 | 2010-09-08 | 深圳市科聚新材料有限公司 | High-heat-resisting glass-fiber reinforced polyester composite material and preparing method |
| CN102786676A (en) * | 2012-08-10 | 2012-11-21 | 金发科技股份有限公司 | Polyester elastomer with branching structure and preparation method thereof |
| CN105324434A (en) * | 2013-07-01 | 2016-02-10 | 株式会社钟化 | High thermal conductivity thermoplastic resin composition with excellent injection moldability |
| US10030138B2 (en) | 2013-07-01 | 2018-07-24 | Kaneka Corporation | High thermal conductivity thermoplastic resin composition with excellent injection moldability |
| CN105754079A (en) * | 2014-11-10 | 2016-07-13 | 财团法人工业技术研究院 | Thermoplastic polyester elastomer and method for forming same |
| US9688813B2 (en) | 2014-11-10 | 2017-06-27 | Industrial Technology Research Institute | Thermoplastic polyester elastomer and method for manufacturing the same |
| CN110444664A (en) * | 2019-08-13 | 2019-11-12 | 昆山维信诺科技有限公司 | A kind of flexible substrate, display panel and its display device |
| CN111073231A (en) * | 2019-12-31 | 2020-04-28 | 聚威工程塑料(上海)有限公司 | PET material with ultrahigh elongation at break and preparation method thereof |
| CN115011081A (en) * | 2022-06-10 | 2022-09-06 | 中广核俊尔(浙江)新材料有限公司 | Glass fiber reinforced PET composition with rapid crystallization and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1079411C (en) | 2002-02-20 |
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