CN101671420B - PET alloy material, special compatibilizer thereof and preparation method thereof - Google Patents

PET alloy material, special compatibilizer thereof and preparation method thereof Download PDF

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CN101671420B
CN101671420B CN2009100930264A CN200910093026A CN101671420B CN 101671420 B CN101671420 B CN 101671420B CN 2009100930264 A CN2009100930264 A CN 2009100930264A CN 200910093026 A CN200910093026 A CN 200910093026A CN 101671420 B CN101671420 B CN 101671420B
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pet
graft copolymer
alloy material
toughner
glycidyl methacrylate
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CN101671420A (en
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葛学武
平翔
汪谟贞
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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Abstract

The invention discloses a radiation grafting compatibilizer modified PET alloy material, a special compatibilizer thereof and a preparation method thereof. The graft copolymer consists of a main chain formed by the structural units shown by formula I and a branched chain formed by the structural units shown by formula II; -CH2- in the formula II is connected with -CH2- in the formula I by chemical bond; and the grafting rate is 0.09-0.18%. The preparation method of the graft copolymer comprises the steps: in inert atmosphere, evenly mixing PET, acrylic acid and polymerization inhibitor and then irradiating to have graft copolymerization reaction, and finally obtaining the graft copolymer; and the irradiation dose rate is 0.8-1.5kGy/h, and the absorbed dose is 20-30kGy. The PET alloy material comprises the components based on parts by weight: 68-85 parts of the PET, 15-20 parts of toughening agent, 0.1-0.2 part of antioxidant and 3-12 parts of the graft copolymer. The PET alloy material is prepared by evenly mixing the components and melt extrusion. The invention not only expands the application of radiation chemistry in the field of preparing PET engineering material, but also provides the PET alloy material with excellent performance, thus having wide application value.

Description

A kind of PET alloy material and dedicated compatibilizer thereof and their preparation method
Technical field
The invention belongs to the engineering plastics field, relate to a kind of PET alloy material and preparation method thereof, particularly a kind of PET alloy material of radiation grafting capacity increasing modifying and dedicated compatibilizer thereof and their preparation method.
Background technology
Thermoplastic polyester polyethylene terephthalate (PET) has light density, high strength, high rigidity, good thermotolerance, chemical proofing, a series of good characteristic such as cheap, and can regeneration, therefore having a wide range of applications in national economy and in national defense industry and the new high-tech industry, is a kind of indispensable type material.PET also is widely used in a plurality of fields such as electronic apparatus, machinery, automobile, medicine equipment except being used for fiber and packing, hollow container etc. after through toughness reinforcing and enhancing.
But, because itself chemical structure and physicals make that its low temperature crystallization speed is slow, and impact property are poor, the molding processing difficulties, the production cycle is long, and this makes PET be subjected to considerable restraint when using as engineering plastics.
In order to improve the toughness of PET, the expert has done a lot of research work both at home and abroad.Traditional method is to use elastomerics to come toughened PET, and uses special alternate expanding material to improve interface compatibility between elastomerics and the PET, to obtain high tenacity PET.As nineteen ninety-five polymkeric substance magazine (Kalfoglou, N.K.; Skafidas, D.S.; Kallitsis, J.K.; Lambert, J.C.; Vanderstappen, L., Comparison of Compatibilizer Effectiveness forPET/HDPE Blends.Polymer 1995,36, (23), in the paper of 4453-4462) delivering, the investigator carries out toughness reinforcing with high density polyethylene(HDPE) to PET, adopt the ethylene-methyl methacrylate glycidyl ester, ethylene-propylene acetoacetic ester-glycidyl methacrylate, maleic anhydride graft thermoplastic elastomer (hydrogenated styrene/Butadiene) segmented copolymer graft copolymers such as (SEBS) is done alternate expanding material, and has obtained good toughening effect.Polymer science was used (Heino, M. in 1997; Kirjava, J.; Hietaoja, P.; Seppala, J., Compatibilization ofpolyethylene terephthalate/polypropylene blends with styrene-ethylene/butylene-styrene (SEBS) block copolymers.J Appl Polym Sci 1997,65, (2), in paper 241-249), the author carries out modification with polypropylene to PET, adopt the SEBS of glycidyl methacrylate graft to do alternate expanding material and toughner, obtained the PET alloy material that performance has bigger improvement.Polymkeric substance magazine (Loyens, W. in 2002; Groeninckx, G., Ultimate mechanical properties of rubber toughened semicrystalline PETat room temperature.Polymer 2002,43, (21), in the paper of 5679-5691) delivering, the investigator carries out toughness reinforcing with ethylene-propylene rubber(EPR) to PET, adopt the ethylene-methyl methacrylate glycidyl ester copolymer to do alternate expanding material, also obtained the PET alloy material that toughness has bigger improvement.
The core technology of these traditional method for toughening is utilized grafted acid anhydrides or epoxy isoreactivity functional group on the elastomerics exactly, hydroxyl or carboxyl functional group generation original position ring-opening reaction with the PET molecule chain end in the polymer blending process form grafting or segmented copolymer, thereby improve the interface compatibility of high polymer alloy, realize improving the purpose of PET material property.The elastomer material that wherein is grafted with functional group all is the method preparation by fusion-grafting or mix monomer copolymerization, and the content of its functional group is generally in 5%.And the reactive functional groups on the PET molecular chain correspondingly is terminal hydroxyl or carboxyl, and wherein carboxyl-content generally is controlled at about 25mol/t when PET resin synthetic.Two kinds of reactive functional groups restrictions quantitatively, reduced reaction efficiency between the two in the melt-processed process, rely on the content of the formed two-phase graft copolymer of this reaction also just to be subjected to certain restriction, caused blend two-phase consistency degree not high thus, thus final decision the over-all properties of PET alloy can not satisfy actual needs.
Summary of the invention
The PET alloy material and dedicated compatibilizer and their preparation method that the purpose of this invention is to provide a kind of radiation grafting capacity increasing modifying.
The expanding material that is used to prepare the PET alloy material provided by the invention is a kind of graft copolymer, the main chain that this multipolymer is made up of structural unit shown in the formula I and be made up of the side chain that structural unit shown in the formula II is formed;
Figure G2009100930264D00021
In the described branched structure unit-CH 2-with described backbone structure unit in-CH 2-link to each other by chemical bond; The percentage of grafting of described graft copolymer is 0.09%-0.18%.
The method of the above-mentioned graft copolymer of preparation provided by the invention, comprise the steps: in inert atmosphere, with PET, contain carboxy vinyl monomer and stopper mixing after, carry out irradiation generation graft copolymerization with the gamma-rays that radioactive substance produced, obtain graft copolymer provided by the invention (PET-g-PAA).
In this method, the dose rate of irradiation is 0.8-1.5kGy/h, and absorption dose is 20-30kGy; Described radioactive substance is 60Co.The described carboxy vinyl monomer that contains is a vinylformic acid; Described stopper is the ionic stopper, and described ionic stopper is FeSO 47H 2O; The reaction solvent of described graft copolymerization is selected distilled water for use.The described weight fraction that contains carboxy vinyl monomer and stopper is respectively 30-40% and 1%.After reaction finishes, also tackle product and do following processing: with distilled water repeatedly flush away be adsorbed on resin surface homopolymer and the oven dry, promptly obtain purified expanding material product.
PET alloy material provided by the invention comprises PET, toughner, oxidation inhibitor and aforementioned graft copolymer provided by the invention.
This PET alloy material also can only be made up of above-mentioned four components.In this alloy material, the effect of graft copolymer is an expanding material.Described toughner is ethylene-methyl acrylate-glycidyl methacrylate copolymer.The parts by weight of each component are respectively: PET:68-85 part, preferred 71-79 part; Toughner: 15-20 part, preferred 15-20 part; Graft copolymer: 3-12 part, the parts by weight of preferred graft copolymer are 3-12, more preferably 6-9 part; In described ethylene-methyl acrylate-glycidyl methacrylate copolymer, the weight fraction of glycidyl methacrylate is 1.5%.
The method of the above-mentioned PET alloy material of preparation provided by the invention comprises the steps: to melt extrude behind PET, toughner, described graft copolymer and the oxidation inhibitor mixing, obtains described PET alloy material;
Described toughner is ethylene-methyl acrylate-glycidyl methacrylate copolymer;
Described oxidation inhibitor is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (1010) and three (2, the 4-di-t-butyl) phenyl-phosphite (168).
Twin screw extruder one district to eight district temperature is respectively 140 ℃, 200 ℃, 255 ℃, 260 ℃, 265 ℃, 265 ℃, 265 ℃ and 265 ℃, and head temperature is 260 ℃.Before reaction, PET, toughner and graft copolymer should be carried out drying.
The radiation grafting of superpolymer is meant under the effect of ionizing rays, makes polymeric main dry polymeric and monomer polymerization reaction take place on side chain generate the process of graft copolymer.Plurality of advantages such as radiation grafting has need not add initiator, technology is simple, product is pure, can react under the normal temperature is a kind of important method to polymer modification.
The present invention utilizes radiation grafted method to prepare a kind of expanding material of the PET of being used for resin toughening, and this expanding material is the polymer chain that has reactable functional group in the grafting of PET resin surface, and the gained graft copolymer is that other method is difficult to realize.This graft copolymer (being expanding material provided by the invention) is joined in the PET co-mixing system, and the epoxide group on the toughner can react with the terminal carboxyl(group) of PET, and PET has been played toughening effect preferably; After adding expanding material provided by the invention (being radiation graft copolymer PET-g-PAA), increased the reaction efficiency of two kinds of functional groups in the melt-processed process, further strengthen incompatible biphase interface compatibility, thereby can prepare the PET alloy material of high comprehensive performance.The present invention has not only opened up the application of radiation chemistry in preparation PET engineering materials field, and a kind of PET alloy material of excellent performance is provided, and is with a wide range of applications.
Description of drawings
Fig. 1 is for adding the SEM photo that expanding material front and back PET alloy notch impacts section.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following embodiment.The trade mark of used PET is CB651 (far spinning Industrial Co., Ltd available from Shanghai) among the following embodiment; Toughner is ethylene-methyl acrylate-glycidyl methacrylate copolymer (ST-2000) (available from Shanghai Xiu Hu chemical industry company limited), and wherein, the content of glycidyl methacrylate is 1.5% (weight fraction), commercially available obtaining; Used oxidation inhibitor is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (1010) and three (2, the 4-di-t-butyl) phenyl-phosphite (168) (available from Nanjing Holley bright science, industry and trade company limited).
By the increase on the PET weight resin before and after the radiation grafting, calculate according to the following equation among the present invention, obtain the percentage of grafting of graft copolymer provided by the invention.
Percentage of grafting=[(W 1-W 0)/W 0] * 100%
In the formula, W 0Be PET weight before reacting, W 1Be the back graft copolymer weight of purifying.
Embodiment 1, preparation graft copolymer (expanding material)
With 60g PET, 14g AAc (vinylformic acid), 0.4g FeSO 47H 2O and 26g distilled water add in the reaction flask and mix, and leave standstill and feed nitrogen deoxygenation and closed reaction vessel after 12 hours.Put into Co-60 source irradiation then, dose rate and absorption dose are respectively 0.8kGy/h and 30kGy.Repeatedly be adsorbed on the homopolymer of resin surface after reaction is finished and dry, obtain expanding material provided by the invention with the distilled water flush away, i.e. PET graft acrylic acid (PET-g-PAA) multipolymer, percentage of grafting is 0.18%.
Embodiment 2, preparation graft copolymer (expanding material)
With 60g PET, 14g AAc (vinylformic acid), 0.4g FeSO 47H 2O and 26g distilled water add in the reaction flask and mix, and leave standstill and feed nitrogen deoxygenation and closed reaction vessel after 12 hours.Put into Co-60 source irradiation then, dose rate and absorption dose are respectively 1.09kGy/h and 25kGy.Repeatedly be adsorbed on the homopolymer of resin surface after reaction is finished and dry, obtain expanding material provided by the invention with the distilled water flush away, i.e. PET graft acrylic acid (PET-g-PAA) multipolymer, percentage of grafting is 0.17%.
Embodiment 3, preparation graft copolymer (expanding material)
With 60g PET, 14g AAc (vinylformic acid), 0.4g FeSO 47H 2O and 26g distilled water add in the reaction flask and mix, and leave standstill and feed nitrogen deoxygenation and closed reaction vessel after 12 hours.Put into Co-60 source irradiation then, dose rate and absorption dose are respectively 1.5kGy/h and 20kGy.Repeatedly be adsorbed on the homopolymer of resin surface after reaction is finished and dry, obtain expanding material provided by the invention with the distilled water flush away, i.e. PET graft acrylic acid (PET-g-PAA) multipolymer, percentage of grafting is 0.09%.
Embodiment 4, preparation PET alloy
With PET, the ST-2000 of oven dry and the PET-g-PAA, 1010 and 168 for preparing of embodiment 1 (in each PET alloy sample of present embodiment, 1010 and 168 consumption is all constant, be respectively 1g and 2g) mix after, join in the TE-35 type twin screw extruder, different components according to the described PET alloy system of table 1, carrying out reactivity melt extrudes, twin screw extruder one district to eight district temperature is respectively 140 ℃, 200 ℃, 255 ℃, 260 ℃, 265 ℃, 265 ℃, 265 ℃ and 265 ℃, and head temperature is 260 ℃.The material of extruding pelletizing after the running water cooling obtains masterbatch; Join after the masterbatch drying in the HTF80X1 type injection moulding machine and carry out injection moulding, obtain being numbered the PET alloy material test bars of 1-5 after the injection moulding respectively.
Table 1, the different PET alloy material of forming
The PET alloy material batten of the above-mentioned 1-5 of being numbered is respectively taken out half at 120 ℃ of following thermal treatment 3h; Afterwards all battens are left in relative humidity and are 50%, temperature is to leave standstill 12h under 25 ℃ the condition, carry out Mechanics Performance Testing again, testing standard and gained mechanical property result are shown in table 2 and table 3, wherein, table 2 is Mechanics Performance Testing result after the PET alloy material thermal treatment of 1-5 for numbering, and table 3 is the contrast of PET alloy material mechanics The performance test results before and after 120 ℃ of thermal treatments of being numbered 1-5; Before being 120 ℃ of thermal treatments before the annealing, promptly refer to 120 ℃ of thermal treatments after the annealing after.The SEM photo (be respectively numbering 1 and numbering 3 samples, respectively corresponding Figure 1A and Figure 1B) of Fig. 1 for adding expanding material front and back PET alloy material notch shock section.As seen from the figure, behind the interpolation expanding material, in the PET alloy, incompatible biphase interface compatibility obviously improves.
PET alloy material mechanical property changes behind table 2, the interpolation expanding material
Figure G2009100930264D00052
The variation of table 3,120 ℃ of thermal treatment front and back PET alloy material Izod notched Izod impact strength
Figure G2009100930264D00053
Embodiment 5, preparation PET alloy
With PET, the ST-2000 of oven dry and the PET-g-PAA, 1010 and 168 for preparing of embodiment 2 (in each PET alloy sample of present embodiment, 1010 and 168 consumption is all constant, be respectively 1g and 2g) mix after, join in the TE-35 type twin screw extruder, different components according to the described PET alloy material of table 4, carrying out reactivity melt extrudes, twin screw extruder one district to eight district temperature is respectively 140 ℃, 200 ℃, 255 ℃, 260 ℃, 265 ℃, 265 ℃, 265 ℃ and 265 ℃, and head temperature is 260 ℃.The material of extruding pelletizing after the running water cooling obtains masterbatch; Join after the masterbatch drying in the HTF80X1 type injection moulding machine and carry out injection moulding, obtain being numbered the PET alloy material test bars of 6-10 after the injection moulding respectively.
The PET alloy material batten of the above-mentioned 6-10 of being numbered is respectively taken out half at 120 ℃ of following thermal treatment 3h; Afterwards all battens are left in relative humidity and are 50%, temperature is to leave standstill 12h under 25 ℃ the condition, carry out Mechanics Performance Testing again, testing standard and gained mechanical property result are shown in table 5 and table 6, wherein, table 5 is Mechanics Performance Testing result after the PET alloy material thermal treatment of 6-10 for numbering, and table 6 is the contrast of PET alloy material mechanics The performance test results before and after 120 ℃ of thermal treatments of numbering 6-10; Before being 120 ℃ of thermal treatments before the annealing, promptly refer to 120 ℃ of thermal treatments after the annealing after.
Table 4, the different PET alloy material of forming
Figure G2009100930264D00061
Behind table 5, the interpolation radiation grafting expanding material, PET alloy material mechanical property changes
Figure G2009100930264D00062
The variation of table 6,120 ℃ of thermal treatment front and back PET alloy material Izod notched Izod impact strength
Figure G2009100930264D00063

Claims (6)

1. a PET alloy material comprises PET, toughner, oxidation inhibitor and graft copolymer;
Described graft copolymer, the main chain of forming by structural unit shown in the formula I and form by the side chain that structural unit shown in the formula II is formed;
(formula I)
Figure FSB00000524092000012
(formula II)
In the described branched structure unit-CH 2-with described backbone structure unit in-CH 2-link to each other by chemical bond; The percentage of grafting of described graft copolymer is 0.09%-0.18%;
Described toughner is ethylene-methyl acrylate-glycidyl methacrylate copolymer;
The parts by weight of each component are respectively:
PET:68-85 part;
Toughner: 15-20 part;
Described graft copolymer: 3-12 part;
In described ethylene-methyl acrylate-glycidyl methacrylate copolymer, the weight percentage of glycidyl methacrylate is 1.5%.
2. material according to claim 1 is characterized in that: described PET alloy material is made up of PET, toughner, oxidation inhibitor and described graft copolymer;
Described toughner is ethylene-methyl acrylate-glycidyl methacrylate copolymer;
The parts by weight of each component are respectively:
PET:68-85 part;
Toughner: 15-20 part;
Oxidation inhibitor: 0.1-0.2 part;
Described graft copolymer: 3-12 part;
In described ethylene-methyl acrylate-glycidyl methacrylate copolymer, the weight percentage of glycidyl methacrylate is 1.5%.
3. material according to claim 2 is characterized in that: described PET alloy material is made up of the component of following parts by weight:
PET:71-79 part;
Toughner: 15-20 part;
Oxidation inhibitor: 0.1-0.2 part;
Described graft copolymer: 6-9 part; In described ethylene-methyl acrylate-glycidyl methacrylate copolymer, the weight percentage of glycidyl methacrylate is 1.5%.
4. method for preparing the arbitrary described PET alloy material of claim 1-3, comprise the steps: PET, toughner, described graft copolymer and oxidation inhibitor mixing with described parts by weight after, melt extrude, obtain described PET alloy material;
Described toughner is ethylene-methyl acrylate-glycidyl methacrylate copolymer;
Described oxidation inhibitor is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and three (2, the 4-di-t-butyl) phenyl-phosphite.
5. method according to claim 4, the described reaction unit that melt extrudes reaction is a twin screw extruder; Described twin screw extruder one district to eight district temperature is respectively 140 ℃, 200 ℃, 255 ℃, 260 ℃, 265 ℃, 265 ℃, 265 ℃ and 265 ℃, and head temperature is 260 ℃.
6. according to claim 4 or 5 described methods, it is characterized in that: described graft copolymer is to be prepared according to the method that comprises the steps: in inert atmosphere, behind PET, vinylformic acid and stopper mixing, carry out irradiation generation graft copolymerization with the gamma-rays that radioactive substance produced, obtain described graft copolymer;
Described stopper is the ionic stopper;
Described vinylformic acid and the stopper weight percentage in radiation grafting is respectively 30-40% and 1%; The dose rate of irradiation is 0.8-1.5kGy/h, and absorption dose is 20-30kGy; Described radioactive substance is 60Co;
Described ionic stopper is FeSO 47H 2O;
The reaction solvent of described graft copolymerization is selected distilled water for use.
CN2009100930264A 2009-09-17 2009-09-17 PET alloy material, special compatibilizer thereof and preparation method thereof Expired - Fee Related CN101671420B (en)

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CN103113721B (en) * 2011-11-17 2016-03-02 上海金发科技发展有限公司 A kind of heat resisting super ductibility polyethylene terephthalate mixture and preparation method thereof
CN107987314B (en) * 2017-11-30 2020-05-19 浙江创摩新材料有限公司 Special compatibilizer suitable for PET/fluoroplastic alloy material and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101054465A (en) * 2007-05-24 2007-10-17 深圳市科聚新材料有限公司 PC/PET alloy and manufacture method thereof
CN101058665A (en) * 2006-04-17 2007-10-24 华东理工大学 Polybutylene terephthalate composite material and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101058665A (en) * 2006-04-17 2007-10-24 华东理工大学 Polybutylene terephthalate composite material and preparation method thereof
CN101054465A (en) * 2007-05-24 2007-10-17 深圳市科聚新材料有限公司 PC/PET alloy and manufacture method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
张振锋、 赵敏等.辐射接枝改性聚酯薄膜表面防雾滴性研究.《中国塑料》.2005,第16卷(第6期),82-85. *
郭锴,李军等.丙烯酸在PET膜表面的紫外光共辐射接枝.《辐射研究于辐射工艺学报》.1999,第17卷(第2期),76-79. *

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