CN101314628A - High-efficiency ultra-low-smell maleic anhydride graft composition - Google Patents

High-efficiency ultra-low-smell maleic anhydride graft composition Download PDF

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Publication number
CN101314628A
CN101314628A CNA2008100398282A CN200810039828A CN101314628A CN 101314628 A CN101314628 A CN 101314628A CN A2008100398282 A CNA2008100398282 A CN A2008100398282A CN 200810039828 A CN200810039828 A CN 200810039828A CN 101314628 A CN101314628 A CN 101314628A
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CN
China
Prior art keywords
maleic anhydride
low
smell
graft composition
anhydride graft
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CNA2008100398282A
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Chinese (zh)
Inventor
孟成铭
杨涛
陈晓东
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Rizhisheng New Technology Development Co Ltd
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Shanghai Rizhisheng New Technology Development Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Rizhisheng New Technology Development Co Ltd filed Critical Shanghai Rizhisheng New Technology Development Co Ltd
Priority to CNA2008100398282A priority Critical patent/CN101314628A/en
Publication of CN101314628A publication Critical patent/CN101314628A/en
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885—Screw or gear
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The invention relates to a preparation method of a high-performance ultra-low-odor maleic anhydride grafted composition by reaction extrusion. The maleic anhydride grafted composition is characterized in that the composition comprises 90wt%-97wt% of polymeric resin, 1wt%-5wt% of maleic anhydride, 0.5wt%-2wt% of initiator, 0.5wt%-1.5wt% of second monomer, 0.5wt%-2wt% of odor absorbent and 0.1wt%-1wt% of antioxidant. The preparation method comprises the steps as follows: weighing the raw materials; mixing in a high speed mixer for 2-5 minutes; discharging; and carrying out fusion reaction and extruding in a twin-screw extruder at a rotation speed of 180-600rpm at 150-225 DEC C. The maleic anhydride grafted composition has the characteristics of high grafting ratio, light color, low gel content and low maleic anhydride residue, and can be widely applied in a high molecular material processing industry.

Description

A kind of high-efficiency ultra-low-smell maleic anhydride graft composition
Technical field
The present invention relates to a kind of high-efficiency ultra-low-smell maleic anhydride graft composition, can be widely used in the processing of high molecular material industry, belong to the polymer modification field.
Background technology
Along with science and technology and development of times, macromolecular material has been applied to every field more and more widely, can better be satisfied with the requirement of product in order to make it, macromolecular material is carried out modification or alloying become a kind of inevitable means, yet because between the various high molecular polymers or polar difference between polymkeric substance and the filling toughener, cause it can better be not compatible, this just needs a kind of high molecular compatible agent to solve the interface problem of two kinds of incompatible polymers.
At present, modal compatilizer is the composition that polyolefine adopts the frit reaction grafted maleic anhydride on the market.But in the process of maleic anhydride grafted polymer, usually be accompanied by the generation of some side reactions, chain rupture such as molecule, crosslinking reaction between the macromole, the rising of gel content, the graft product color and luster is yellow partially, and is accompanied by the residual of initiator and maleic anhydride, and the maleic anhydride residual volume can produce irritating smell greatly in the course of processing, impair one's health, bring defectives such as bubble, smell and variable color simultaneously to goods.Unreacted initiator can have a negative impact to the performance of product simultaneously, can quicken polyolefinic thermal destruction in the course of processing.Therefore the maleic anhydride grafted polymer of developing a kind of efficient low smell will have very wide application prospect and industrial value.
Summary of the invention
The purpose of this invention is to provide a kind of have percentage of grafting height, ultra-low-smell, lighter color, gel content is low, the maleic anhydride residual volume is few high-efficiency ultra-low-smell maleic anhydride graft composition.
For realizing above purpose, technical scheme of the present invention provides a kind of high-efficiency ultra-low-smell maleic anhydride graft composition, it is characterized in that, form by following weight percent raw material: fluoropolymer resin 90-97%, maleic anhydride 1-5%, initiator 0.5-2%, the second monomer 0.5-1.5%, odour absorbents 0.5-2%, oxidation inhibitor 0.1-1%.
Described fluoropolymer resin is polyethylene, polypropylene, ethylene-octene copolymer or Ethylene Propylene Terpolymer copolymerization;
Described maleic anhydride is the colourless crystallization body, and irritating smell is arranged, 52.8 ℃ at zero pour, 202 ℃ of boiling points; Described initiator is dicumyl peroxide or dibenzoyl peroxide; Described second monomer is vinylbenzene or vinyl acetate; Described oxidation inhibitor is the compound system of a kind of Hinered phenols antioxidant and phosphite ester kind antioxidant, can be 168/1010 (1: 1), 1010 be four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, 168 is (2,4 di-tert-butyl-phenyl) tris phosphite.
A kind of preparation method of high-efficiency ultra-low-smell maleic anhydride graft composition, it is characterized in that, its preparation method is as follows: the raw material that takes by weighing was by weight percentage put into high-speed mixer and mixing 2-5 minute, discharging, use the twin screw extruder extruding pelletization then, processing temperature is at 150-225 ℃, and the screw rod revolution is at 180-600 rev/min.
Segmentation One section Two sections Three sections Four sections Five sections Six sections Seven sections Eight sections Nine sections
Processing temperature ℃ 150 160 180 200 220 220 215 210 200
Its major technique is to control each section of extrusion reaction device screw combinations, makes initiator, and maleic anhydride reacts completely, and reduces residual volume.
Polyethylene, polypropylene, ethylene-octene copolymer and ternary ethylene-propylene copolymer itself do not have polarity, and maleic anhydride graft has been given these polymer polarity to these main polymer chains, become the compatilizer that has more use value.
Initiator mainly is the generation that impels graft reaction, grafted monomer mainly is to suppress macromolecular autohemagglutination as second monomer, oxidation inhibitor is the compound system of a kind of Hinered phenols antioxidant and phosphite ester kind antioxidant, can improve composition in the antioxidant property of the course of processing and the ageing resistance in the use.
Make reaction by aforesaid method and extrude the preparation high-efficiency ultra-low-smell maleic anhydride graft composition, it is low well to have solved on the market compatilizer percentage of grafting, color and luster Huang, scent of, gel content height, the shortcoming that the maleic anhydride residual volume is big.Having prepared one group has percentage of grafting height, ultra-low-smell, lighter color, gel content reaction low, that the maleic anhydride residual volume is few and extrudes the preparation high-efficiency ultra-low-smell maleic anhydride graft composition.
Characteristics such as advantage of the present invention is percentage of grafting height, ultra-low-smell, lighter color, gel content is low, the maleic anhydride residual volume is few can be widely used in the processing of high molecular material industry.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1-6:
Material name Embodiment 1 (wt%) Comparative Examples 1 (wt%) Embodiment 2 (wt%) Comparative Examples 2 (wt%) Embodiment 3 (wt%) Comparative Examples 3 (wt%)
Polypropylene 94 96.5 / / / /
Ethylene-octene copolymer / / 94 96.5 / /
Ternary ethylene-propylene copolymer / / / / 94 96.5
Maleic anhydride 2 2 2 2 2 2
Dicumyl peroxide 1 1 1 1 1 1
Vinylbenzene 1 / 1 / 1 /
Odour absorbents 1.5 / 1.5 / 1.5 /
Oxidation inhibitor 0.5 0.5 0.5 0.5 0.5 0.5
Said components was put into high-speed mixer and mixing 2-5 minute in proportion, and the screw extrusion press extruding pelletization is used in discharging then, and processing temperature is at 150-225 ℃, and the screw rod revolution is at 180-600 rev/min.
Segmentation One section Two sections Three sections Four sections Five sections Six sections Seven sections Eight sections Nine sections
Processing temperature ℃ 150 160 180 200 220 220 215 210 200
According to sample 1-3 and the Comparative Examples 1-3 that embodiment and Comparative Examples make, adopt acid base titration to record its percentage of grafting, with range estimation with smell and hear its color and luster of judgement and smell.
Test performance contrast (table 2)
Project Sample 1 Comparative sample 1 Sample 2 Comparative sample 2 Sample 3 Comparative sample 3
Percentage of grafting % 1.6 1.0 1.5 1.0 1.5 1.0
Color and luster Raw white Yellow Little Huang Yellow Little Huang Yellow
Smell Do not have Scent of Slightly Scent of Slightly Scent of

Claims (7)

1. a high-efficiency ultra-low-smell maleic anhydride graft composition is characterized in that, is made up of following weight percent raw material: fluoropolymer resin 90-97%, maleic anhydride 1-5%, initiator 0.5-2%, the second monomer 0.5-1.5%, odour absorbents 0.5-2%, oxidation inhibitor 0.1-1%.
2. according to claims 1 described a kind of high-efficiency ultra-low-smell maleic anhydride graft composition, it is characterized in that: described fluoropolymer resin is polyethylene, polypropylene, ethylene-octene copolymer or ternary ethylene-propylene copolymer.
3. according to claims 1 described a kind of high-efficiency ultra-low-smell maleic anhydride graft composition thing, it is characterized in that described maleic anhydride is the colourless crystallization body, and irritating smell is arranged, 52.8 ℃ at zero pour, 202 ℃ of boiling points.
4. according to claims 1 described a kind of high-efficiency ultra-low-smell maleic anhydride graft composition, it is characterized in that described initiator is dicumyl peroxide or dibenzoyl peroxide.
5. according to claims 1 described a kind of high-efficiency ultra-low-smell maleic anhydride graft composition, it is characterized in that described second monomer is vinylbenzene or vinyl acetate.
6. according to claims 1 described a kind of high-efficiency ultra-low-smell maleic anhydride graft composition, it is characterized in that, described oxidation inhibitor is the compound system of a kind of Hinered phenols antioxidant and phosphite ester kind antioxidant, be 1: 1 168/1010 composite, 1010 is four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, 168 is (2,4 di-tert-butyl-phenyl) tris phosphite.
7. according to claims 1 described a kind of high-efficiency ultra-low-smell maleic anhydride graft composition, it is characterized in that, its preparation method is as follows: the raw material that takes by weighing was by weight percentage put into high-speed mixer and mixing 2-5 minute, discharging, use the twin screw extruder extruding pelletization then, processing temperature is at 150-225 ℃, and the screw rod revolution is at 180-600 rev/min.
CNA2008100398282A 2008-06-30 2008-06-30 High-efficiency ultra-low-smell maleic anhydride graft composition Pending CN101314628A (en)

Priority Applications (1)

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CNA2008100398282A CN101314628A (en) 2008-06-30 2008-06-30 High-efficiency ultra-low-smell maleic anhydride graft composition

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102399312A (en) * 2011-11-24 2012-04-04 上海日之升新技术发展有限公司 Slowly-released peroxide initiating system with nano structure and preparation method thereof
CN102558837A (en) * 2010-12-21 2012-07-11 上海日之升新技术发展有限公司 Low temperature impact resistant nylon flexibilizer and preparation method of low temperature impact resistant nylon flexibilizer
CN102643391A (en) * 2012-04-19 2012-08-22 深圳市科聚新材料有限公司 Ethylene propylene diene monomer grafted maleic anhydride and preparation method thereof
CN102702661A (en) * 2012-06-05 2012-10-03 广州市合诚化学有限公司 Antioxidant polypropylene compatilizer and preparation method and application thereof
CN103289278A (en) * 2012-02-23 2013-09-11 苏州井上高分子新材料有限公司 Modified polyolefin cable material achieving controllable grafting ratio
WO2014000654A1 (en) * 2012-06-27 2014-01-03 深圳市科聚新材料有限公司 Low-odour polypropene grafted maleic anhydride extruded in twin-screw extruder and method for preparing same
CN109265612A (en) * 2018-08-01 2019-01-25 南京京锦元科技实业有限公司 A kind of low smell maleic anhydride of high grafting rate is grafted PE
CN109535327A (en) * 2018-12-13 2019-03-29 沈阳科通塑胶有限公司 A kind of maleic anhydride-grafted polypropylene material and preparation method thereof of low smell high fusion index
CN110156929A (en) * 2019-05-08 2019-08-23 武汉理工大学 A kind of ethylene propylene diene rubber strengthening agent and its preparation method and application
CN113651917A (en) * 2021-10-19 2021-11-16 北京能之光科技有限公司 Method for improving grafting rate of low-odor maleic anhydride grafted polyolefin for automobile
WO2022056586A1 (en) * 2020-09-15 2022-03-24 Victamax Limited Plastic resin modifier compositions and methods for preparing thermoplastic materials and articles using the same

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102558837A (en) * 2010-12-21 2012-07-11 上海日之升新技术发展有限公司 Low temperature impact resistant nylon flexibilizer and preparation method of low temperature impact resistant nylon flexibilizer
CN102399312A (en) * 2011-11-24 2012-04-04 上海日之升新技术发展有限公司 Slowly-released peroxide initiating system with nano structure and preparation method thereof
CN102399312B (en) * 2011-11-24 2013-07-03 上海日之升新技术发展有限公司 Slowly-released peroxide initiating system with nano structure and preparation method thereof
CN103289278A (en) * 2012-02-23 2013-09-11 苏州井上高分子新材料有限公司 Modified polyolefin cable material achieving controllable grafting ratio
CN102643391A (en) * 2012-04-19 2012-08-22 深圳市科聚新材料有限公司 Ethylene propylene diene monomer grafted maleic anhydride and preparation method thereof
WO2013155961A1 (en) * 2012-04-19 2013-10-24 深圳市科聚新材料有限公司 Ethylene-propylene-diene monomer grafted maleic anhydride and preparation method therefor
CN102702661A (en) * 2012-06-05 2012-10-03 广州市合诚化学有限公司 Antioxidant polypropylene compatilizer and preparation method and application thereof
CN102702661B (en) * 2012-06-05 2013-10-16 广州市合诚化学有限公司 Antioxidant polypropylene compatilizer and preparation method and application thereof
WO2014000654A1 (en) * 2012-06-27 2014-01-03 深圳市科聚新材料有限公司 Low-odour polypropene grafted maleic anhydride extruded in twin-screw extruder and method for preparing same
CN109265612A (en) * 2018-08-01 2019-01-25 南京京锦元科技实业有限公司 A kind of low smell maleic anhydride of high grafting rate is grafted PE
CN109535327A (en) * 2018-12-13 2019-03-29 沈阳科通塑胶有限公司 A kind of maleic anhydride-grafted polypropylene material and preparation method thereof of low smell high fusion index
CN110156929A (en) * 2019-05-08 2019-08-23 武汉理工大学 A kind of ethylene propylene diene rubber strengthening agent and its preparation method and application
CN110156929B (en) * 2019-05-08 2022-01-04 武汉理工大学 Ethylene propylene diene monomer reinforcing agent and preparation method and application thereof
WO2022056586A1 (en) * 2020-09-15 2022-03-24 Victamax Limited Plastic resin modifier compositions and methods for preparing thermoplastic materials and articles using the same
CN116419948A (en) * 2020-09-15 2023-07-11 华海科技有限公司 Plastic resin modifier composition and method for preparing thermoplastic materials and articles using the same
CN113651917A (en) * 2021-10-19 2021-11-16 北京能之光科技有限公司 Method for improving grafting rate of low-odor maleic anhydride grafted polyolefin for automobile

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Open date: 20081203