CN102391405A - Nucleating agent for polyethylene terephthalate and preparation method as well as application thereof - Google Patents
Nucleating agent for polyethylene terephthalate and preparation method as well as application thereof Download PDFInfo
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- CN102391405A CN102391405A CN2011102477261A CN201110247726A CN102391405A CN 102391405 A CN102391405 A CN 102391405A CN 2011102477261 A CN2011102477261 A CN 2011102477261A CN 201110247726 A CN201110247726 A CN 201110247726A CN 102391405 A CN102391405 A CN 102391405A
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- nucleator
- vinylbenzene
- methylacrylic acid
- polyethyleneterephthalate
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Abstract
The invention provides a nucleating agent for polyethylene terephthalate and a preparation method as well as application thereof. The nucleating agent is copolymer of styrene and methacrylic acid or copolymer of styrene and methacrylate. The nucleating agent has the advantages that: less amount of nucleating agent, only 0.1 percent, is added; and the crystallization rate of the polyethylene terephthalate (PET) is obviously increased (the crystallization initial temperature is increased by 12.1 DEG C). After the nucleating agent is added, the crystallinity of the PET is increased by over 30 percent; after the nucleating agent is added, characteristic viscosity of the PET is basically unchanged; and thus, the defect of large influence of an organic nucleating agent such as sodium benzoate and the like on the characteristic viscosity of the PET is overcome, and the mechanical property of the PET is also obviously improved.
Description
Technical field
The present invention relates to a kind of nucleator as polyethyleneterephthalate, be specifically related to a kind of methylacrylic acid-vinylbenzene and salt thereof as polyethyleneterephthalate crystallization nucleating agent and preparation method thereof.
Background technology
Polyethyleneterephthalate (PET) is nineteen fifty-three to realize industrialized linear thermoplastic's semi-crystalline polymer the earliest by DuPont company.Its melt temperature (T
m) and second-order transition temperature (T
g) higher; Have good thermotolerance, creep resistance, resistance to fatigue, rub resistance and abradability, electrical insulating property and chemical proofing; And production energy consumption is low, and processing characteristics is good, is widely used in fields such as synthon, film, engineering plastics, medicine and daily necessities.PET as the subject matter of engineering plastics is: second-order transition temperature is high, the nucleation ability, and crystallization rate is slow, processing Mo Wengao, shaping cycle and mechanical property and resistance toheat are low etc., and therefore, PET is slow as the application development of engineering plastics.In order to give full play to the PET high-performance, advantage must be improved its crystal property cheaply, manages to increase its crystallization velocity, improves the percent crystallinity of product.Method to the crystal property modification of PET generally is to add nucleator or nucleation accelerating agent, reaches the effect of accelerating the PET crystallization rate.
The PET nucleator is of a great variety, generally can be divided into mineral-type, organic type and high score subclass nucleator.The mineral-type nucleator mainly comprises inorganic salt, MOX; Organic class mainly comprises monocarboxylic Na, Li, Ca salt, aromatic hydroxyl sulphonate etc.; The high score subclass mainly comprises an alkali metal salt of polyester oligomer, Wholly aromatic polyester powder, ionic polymer etc.
Patent documentation CN101709121A discloses a kind of composite nucleating agent, mainly comprises the Surlyn and the Sodium Benzoate of super finely ground slag, solid polyethylene glycol, E.I.Du Pont Company, has crystallization rate and the heat-stable effect of accelerating PET.CN1386783A discloses a kind of dehydrogenated metallic abietate that is extracted by nilox resin, and the crystallization of PET is also had promoter action.Chemical reaction at high temperature takes place in the effect that existing this type nucleator reaches nucleation normally nucleator and PET, generates the PET-COONa ionic polymer, and this type ionic polymer can quicken the PET crystallization as the nuclei of crystallization.But because chemical reaction, the PET molecular chain is destroyed, and the molecular weight of polymkeric substance reduces, and causes the mechanical properties decrease of converted products.
In order to improve the problem that existing nucleator exists; Patent documentation CN102020756A discloses a kind of aromatic dicarboxylic acid salt and the cinnamic segmented copolymer nucleator as PET; Add a spot of this nucleator and not only effectively raise the crystal property of PET; Less to the influence of viscosity simultaneously, played the effect of similar chainextender, but there are shortcomings such as the more yield of synthesis step is low in this method.
The PET nucleator Surlyn of du pont company production is the random copolymers of ethene and methylacrylic acid, forms ionomer through the part neutralization, can effectively improve the crystallization rate of PET.But its influence to the PET viscosity-average molecular weight is bigger.
Summary of the invention
The object of the present invention is to provide a kind of nucleator that is used for polyethyleneterephthalate, to overcome the problem that exists in the prior art.
The described nucleator that is used for polyethyleneterephthalate is characterized in that, is the multipolymer of a kind of vinylbenzene and methylacrylic acid;
Or do;
The salt of the multipolymer of vinylbenzene and methylacrylic acid;
The multipolymer of said vinylbenzene and methylacrylic acid is characterized by, and the mass ratio of vinylbenzene and methylacrylic acid is 4～25; Preferably 6～10;
The salt of the multipolymer of said vinylbenzene and methylacrylic acid is characterized by, and the mass ratio of vinylbenzene and methacrylate is 2.7～24, and preferably 4.2～10; Said methacrylate wherein, contains quality and is 45～99% methacrylate, and all the other are methylacrylic acid, and the mass content of preferred methacrylate is 75～95%;
Described salt is sodium salt or sylvite;
The preparation method of said polyethyleneterephthalate nucleator comprises the steps:
In solvent, add vinylbenzene and methylacrylic acid, under initiator causes, 75～85 ℃ of following polyreactions 5～10 hours;
Polymers soln is changed in the precipitation solvent, and deposition is filtered the collecting precipitation thing, and drying precipitate obtains described vinylbenzene and Sipacril 2739OF;
Perhaps, in solvent, add vinylbenzene and methylacrylic acid, initiator causes down, 75～85 ℃ of following polyreactions 5～10 hours, neutralizes with alkali then;
Polymers soln is changed in the precipitation solvent, and deposition is filtered then, and filter cake obtains the salt of the multipolymer of described vinylbenzene and methylacrylic acid through drying;
Described initiator is selected from azo-bis-isobutyl cyanide or Lucidol;
Described solvent is selected from benzene, dioxane, butylacetate or toluene;
Described precipitation solvent is selected from sherwood oil, methyl alcohol or water;
The mass ratio of vinylbenzene and methylacrylic acid is 5～25; Preferred mass ratio is 5～10;
The consumption of solvent is that to make the total mass concentration of monomer be 10～30wt%;
Initiator amount is 0.5～5.0wt% of the total quality of monomer;
The consumption of precipitation solvent is monomer and solvent total mass 4～8 times;
The quality that said monomer is total refers to the total mass of vinylbenzene and methylacrylic acid;
Described alkali is NaOH or KOH, and it is better that alkali is dissolved in the methyl alcohol result of use, preferably uses the rosaline solution of alkali concn 0.5～1mol/L.
The described nucleator that is used for polyethyleneterephthalate can be used as nucleator, is used to prepare polyethyleneterephthalate, and its preferred addition is 0.1～5% of a polyethyleneterephthalate quality.
Polyethyleneterephthalate nucleator advantage provided by the invention is:
1 nucleator addition of the present invention is less, only adds 0.1%, the crystallization rate of polyethyleneterephthalate (PET) be significantly improved (crystallization onset temperature improve 12.1 ℃).
2 add nucleator of the present invention after, the percent crystallinity of PET be significantly improved (improving more than 30%).
After the 3 interpolations nucleator of the present invention, the intrinsic viscosity of PET is constant basically, therefore overcome organic type of nucleators such as Sodium Benzoate to the bigger defective of PET intrinsic viscosity influence, and the mechanical property of PET is significantly improved also.
Description of drawings
Fig. 1 is embodiment 2 PS-methylacrylic acid infrared spectrum.
Fig. 2 is the infrared spectrum of embodiment 2 PS-sodium methacrylate nucleator.
Embodiment
Below in conjunction with specific embodiment the present invention is elaborated.Composition umber wherein by weight.
The measuring method of each item index of the present invention and evaluation method:
1) DSC test
With 1～5 part of PET100 part, the nucleator of the Yizheng Fiber Optical plant SB500 trade mark, go up banburying at HAAKE (Polylab RC 300P), the blend time is 6min, and rotating speed is 80rpm, and blending temperature is 265 ℃.Close experienced sample liquid nitrogen quenching behind 300 ℃ of fusion 5min places among the DSC DSC (Netzsch, DSC 200 F3) this quenching appearance with 10 ℃/min to be warming up to 300 ℃ from 20 ℃, from this DSC curve, obtains second-order transition temperature (T
g) and cold crystallization temperature (T
Cc).Or placing DSC to be warming up to 300 ℃ the PET sample with 50 ℃/min, constant temperature 5min is cooled to 50 ℃ with 10 ℃/min after eliminating thermal history, obtains the melt crystallization temperature (T of sample
Mc).
2) chemical titration
Get a certain amount of multipolymer that gets, be dissolved in the THF, use the NaOH/CH of 0.1mol/L then
3The titration of OH solution is an indicator with phenolphthalein, and then tries to achieve the content of vinylformic acid in multipolymer.
3) limiting viscosity [η]
The PET sample is dissolved in phenol-tetrachloroethane mixing solutions (mass ratio 1: 1), and concentration is about 5mg/mL, and is following to determination of ubbelohde viscometer intrinsic viscosity [η] in 25 ℃.
Embodiment 1
With 2g methylacrylic acid and 46g vinylbenzene, place the benzene of 320g, be warming up to 80 ℃, add the 0.48g azo-bis-isobutyl cyanide, reaction 6h gets the copolymer solution of vinylbenzene and methylacrylic acid; Adding NaOH concentration is the methanol solution 23.5mL of 1mol/L, pours in the sherwood oil of 1600g, gets white precipitate, gets the white powder nucleator behind filtration, the vacuum-drying 24h.
The mass ratio that chemical titration records styrene/methacrylic acid in the multipolymer of vinylbenzene-methylacrylic acid is 20.3;
The degree of neutralization of methylacrylic acid is 100% in the nucleator, the mass ratio 16.1 of styrene/methacrylic acid sodium in the nucleator.
After the DSC test result shows adding nucleator of the present invention, add the cold crystallization peak temperature T of the PET sample of 1 portion of nucleator
Cc=122.5, thermal crystalline peak temperature T
Mc=209.8, its intrinsic viscosity is seen table 1.
Embodiment 2
With 10g methylacrylic acid and 48g vinylbenzene, place the benzene of 320g, be warming up to 80 ℃, add the 0.58g azo-bis-isobutyl cyanide, react 6h, get the copolymer solution of vinylbenzene and methylacrylic acid; Adding NaOH concentration is the methanol solution 117mL of 1mol/L, pours in the sherwood oil of 1600g, gets white precipitate, gets the white powder nucleator behind filtration, the vacuum-drying 24h.
The mass ratio that chemical titration records styrene/methacrylic acid in the multipolymer of vinylbenzene-methylacrylic acid is 8.4; Its infared spectrum is seen Fig. 1.
The degree of neutralization of methylacrylic acid is 100% in the nucleator, the mass ratio 6.7 of styrene/methacrylic acid sodium in the nucleator; Its infared spectrum is seen accompanying drawing 2.
After the DSC test result shows adding nucleator of the present invention, add the cold crystallization peak temperature T of the PET sample of 1 portion of nucleator
Cc=118.5, thermal crystalline peak temperature T
Mc=213.1, its intrinsic viscosity is seen table 1.
Embodiment 3
According to the method for embodiment 2, different is that initiator is a Lucidol, and the reaction times is 9h.
The mass ratio that chemical titration records styrene/methacrylic acid in the multipolymer of vinylbenzene-methylacrylic acid is 8.3;
The degree of neutralization of methylacrylic acid is 100% in the nucleator, the mass ratio 6.6 of styrene/methacrylic acid sodium in the nucleator.
After the DSC test result shows adding nucleator of the present invention, add the cold crystallization peak temperature T of the PET sample of 5 portions of nucleators
Cc=114.8, thermal crystalline peak temperature T
Mc=214.3, its intrinsic viscosity is seen table 1.
Embodiment 4
According to the method for embodiment 2, different is to add the 2.9g azo-bis-isobutyl cyanide, with the NaOH methanol solution 233mL of 0.5mol/L concentration.
The mass ratio that chemical titration records styrene/methacrylic acid in the multipolymer of vinylbenzene-methylacrylic acid is 9.5;
The degree of neutralization of methylacrylic acid is 100% in the nucleator, the mass ratio 7.6 of styrene/methacrylic acid sodium in the nucleator.
After the DSC test result shows adding nucleator of the present invention, add the cold crystallization peak temperature T of the PET sample of 1 portion of nucleator
Cc=121.4, thermal crystalline peak temperature T
Mc=211.2, its intrinsic viscosity is seen table 1.
Embodiment 5
According to the method for embodiment 2, different is to add toluene solvant, and the consumption of toluene is 195g.
The mass ratio that chemical titration records styrene/methacrylic acid in the multipolymer of vinylbenzene-methylacrylic acid is 9.0;
The degree of neutralization of methylacrylic acid is 100% in the nucleator, the mass ratio 7.2 of styrene/methacrylic acid sodium in the nucleator.
After the DSC test result shows adding nucleator of the present invention, add the cold crystallization peak temperature T of the PET sample of 1 portion of nucleator
Cc=124.3, thermal crystalline peak temperature T
Mc=210.6, its intrinsic viscosity is seen table 1.
Embodiment 6
According to the method for embodiment 2, different is that methyl alcohol replaces sherwood oil, and the consumption of methyl alcohol is 3000g.
The mass ratio that chemical titration records styrene/methacrylic acid in the multipolymer of vinylbenzene-methylacrylic acid is 8.9;
The degree of neutralization of methylacrylic acid is 100% in the nucleator, the mass ratio 7.1 of styrene/methacrylic acid sodium in the nucleator.
After the DSC test result shows adding nucleator of the present invention, add the cold crystallization peak temperature T of the PET sample of 1 portion of nucleator
Cc=123.9, thermal crystalline peak temperature T
Mc=210.8, its intrinsic viscosity is seen table 1.
Embodiment 7
According to the method for embodiment 2, different is to use the methanol solution neutralization of KOH concentration as 1mol/L.
The mass ratio that chemical titration records styrene/methacrylic acid in the multipolymer of vinylbenzene-methylacrylic acid is 8.4;
The degree of neutralization of methylacrylic acid is 100% in the nucleator, the mass ratio 5.8 of styrene/methacrylic acid potassium in the nucleator.
After the DSC test result shows adding nucleator of the present invention, add the cold crystallization peak temperature T of the PET sample of 1 portion of nucleator
Cc=127.4, thermal crystalline peak temperature T
Mc=209.5.Its intrinsic viscosity is seen table 1.
Embodiment 8
With 10g methylacrylic acid and 48g vinylbenzene, be dissolved in the butylacetate of 320g, be warming up to 80 ℃, add the 0.58g azo-bis-isobutyl cyanide, reaction 6h gets the copolymer solution of vinylbenzene-methylacrylic acid; Adding NaOH concentration is the methanol solution 58.5mL of 1mol/L, pours into while hot in the water of 1600g, gets white precipitate, gets the white powder nucleator behind filtration, the vacuum-drying 24h.
The mass ratio that chemical titration records styrene/methacrylic acid in the multipolymer of vinylbenzene-methylacrylic acid is 7.5;
The degree of neutralization of methylacrylic acid is 50% in the nucleator, and the mass ratio of styrene/methacrylic acid sodium is 13.5 in the nucleator, and the mass ratio of styrene/methacrylic acid is 17.0.
After the DSC test result shows adding nucleator of the present invention, add the cold crystallization peak temperature T of the PET sample of 1 portion of nucleator
Cc=123.6, thermal crystalline peak temperature T
Mc=211.2, its intrinsic viscosity is seen table 1.
The application implementation example
Application test: with 1～5 part of PET100 part, the nucleator of the Yizheng Fiber Optical plant SB500 trade mark; With twin screw extruder (Chemical Machinery Research Institute of Ministry of Chemical Industry; TE-34) mixing granulation (255 ℃ of medial temperatures), (shake moral plastics machinery Co., Ltd., Factory is injection molded into batten on CJ80M3V) at injection moulding machine then; Tensile strength is pressed the GB/T1040-2006 test, and bending strength is pressed the GB/T9341-2008 test.
Used prescription and PET performance are listed in table 1.
PET performance table after the table 1 adding nucleator
Can find out that from table 1 intrinsic viscosity value nucleator of the present invention is in the PET course of processing, the minimum PET that causes degrades.And mechanical property also is significantly improved.
Claims (10)
1. be used for the nucleator of polyethyleneterephthalate, it is characterized in that, be the multipolymer of vinylbenzene and methylacrylic acid; Or be the salt of the multipolymer of vinylbenzene and methylacrylic acid.
2. the nucleator that is used for polyethyleneterephthalate according to claim 1 is characterized in that, the mass ratio of vinylbenzene and methylacrylic acid is 4～25; The mass ratio of vinylbenzene and methacrylate is 2.7～24.
3. the nucleator that is used for polyethyleneterephthalate according to claim 2 is characterized in that, the mass ratio of vinylbenzene and methylacrylic acid is 6～10; The mass ratio of vinylbenzene and methacrylate is 4.2～10.
4. according to claim 1, the 2 or 3 described nucleators that are used for polyethyleneterephthalate, it is characterized in that described salt is sodium salt or sylvite.
5. according to claim 1, the 2 or 3 described nucleators that are used for polyethyleneterephthalate, it is characterized in that said methacrylate wherein, contains quality and be 45～99% methacrylate, all the other are methylacrylic acid.
6. the nucleator that is used for polyethyleneterephthalate according to claim 4 is characterized in that, said methacrylate wherein, contains quality and be 75～95% methacrylate, and all the other are methylacrylic acid.
7. according to each described preparation method who is used for the nucleator of polyethyleneterephthalate of claim 1～6, it is characterized in that, comprise the steps:
In solvent, add vinylbenzene and methylacrylic acid, under initiator causes, 75～85 ℃ of following polyreactions 5～10 hours;
Polymers soln is changed in the precipitation solvent, and deposition is filtered the collecting precipitation thing, and drying precipitate obtains described vinylbenzene and Sipacril 2739OF;
Perhaps, in solvent, add vinylbenzene and methylacrylic acid, add initiator,, neutralize with alkali then 75～85 ℃ of following polyreactions 5～10 hours;
Polymers soln is changed in the precipitation solvent, and deposition is filtered then, and filter cake obtains the salt of the multipolymer of described vinylbenzene and methylacrylic acid through drying.
8. method according to claim 7 is characterized in that described initiator is selected from azo-bis-isobutyl cyanide or Lucidol; Described solvent is selected from benzene, dioxane, butylacetate or toluene; Described precipitation solvent is selected from sherwood oil, methyl alcohol or water; The mass ratio of vinylbenzene and methylacrylic acid is 5～25; Preferred mass ratio is 5～10; The consumption of solvent is that to make the total mass concentration of monomer be 10～30wt%; Initiator amount is 0.5～5.0wt% of the total quality of monomer;
The consumption of precipitation solvent is monomer and solvent total mass 4～8 times; Described alkali is NaOH or KOH, and it is better that alkali is dissolved in the methyl alcohol result of use, preferably uses the rosaline solution of alkali concn 0.5～1mol/L.
9. according to each described application that is used for the nucleator of polyethyleneterephthalate of claim 1～6, it is characterized in that,, be used for the polyethyleneterephthalate processing products as nucleator.
10. application according to claim 9 is characterized in that, addition is 0.1～5% of a polyethyleneterephthalate quality.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102477261A CN102391405A (en) | 2011-08-26 | 2011-08-26 | Nucleating agent for polyethylene terephthalate and preparation method as well as application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102477261A CN102391405A (en) | 2011-08-26 | 2011-08-26 | Nucleating agent for polyethylene terephthalate and preparation method as well as application thereof |
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| CN102391405A true CN102391405A (en) | 2012-03-28 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674921A (en) * | 2016-12-09 | 2017-05-17 | 浙江大学 | Polyester self-nucleating agent as well as preparation method and application thereof |
| CN114685974A (en) * | 2020-12-30 | 2022-07-01 | 广东美的白色家电技术创新中心有限公司 | Nylon composite material, preparation method thereof, injection molded part and household appliance |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1291620A (en) * | 2000-04-24 | 2001-04-18 | 中国科学院化学研究所 | Application of monocarboxyl terephthalate |
| CN101348535A (en) * | 2007-07-17 | 2009-01-21 | 广州金发科技股份有限公司 | Macromole nucleating agent for polypropylene |
-
2011
- 2011-08-26 CN CN2011102477261A patent/CN102391405A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1291620A (en) * | 2000-04-24 | 2001-04-18 | 中国科学院化学研究所 | Application of monocarboxyl terephthalate |
| CN101348535A (en) * | 2007-07-17 | 2009-01-21 | 广州金发科技股份有限公司 | Macromole nucleating agent for polypropylene |
Non-Patent Citations (1)
| Title |
|---|
| SADEGHI, SAYED MOHAMMAD TAGHI: "Synthesis, characterization and thermal stability study of styrene-based ionomers I）programmed heating experiments(10℃/min to 500℃)", 《IRANIAN JOURNAL OF CHEMISTRY & CHEMICAL ENGINEERING-INTERNATIONAL ENGLISH EDITION》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674921A (en) * | 2016-12-09 | 2017-05-17 | 浙江大学 | Polyester self-nucleating agent as well as preparation method and application thereof |
| CN106674921B (en) * | 2016-12-09 | 2018-10-19 | 浙江大学 | A kind of polyester spontaneous nucleation agent and its preparation method and application |
| CN114685974A (en) * | 2020-12-30 | 2022-07-01 | 广东美的白色家电技术创新中心有限公司 | Nylon composite material, preparation method thereof, injection molded part and household appliance |
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Application publication date: 20120328 |