CN101157739A - Method for preparing macromolecule material chain extender - Google Patents
Method for preparing macromolecule material chain extender Download PDFInfo
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- CN101157739A CN101157739A CNA2006101404099A CN200610140409A CN101157739A CN 101157739 A CN101157739 A CN 101157739A CN A2006101404099 A CNA2006101404099 A CN A2006101404099A CN 200610140409 A CN200610140409 A CN 200610140409A CN 101157739 A CN101157739 A CN 101157739A
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Abstract
The present invention relates to a high polymer material chain extender and a preparation method thereof, the components and the contents (weight parts) of the chain extender include: 50 to 75 parts of styrene monomer, 50 to 25 parts of acrylic acid glyceryl ester monomer, 0.1 to 1.2 parts of initiator, 0.1 to 1.0 part of dispersant and 0.1 to 0.3 part of other additives; the preparation method of the chain extender comprises that the reaction monomers and the additives are chosen, the monomers and the additives are added into a reactor according to a set sequence and a copolymerization reaction is carried out under the appropriate temperature and the stirring speed; the final product can be formed by washing and drying the reaction product. Compared with the prior art, the present invention is characterized by simple process, relative higher molecular weight, easy post-treatment, safety, reliability, broader usage and so on.
Description
Technical field
The present invention relates to a kind of preparation method of macromolecule material chain extender, relate in particular to and the macromolecular material that contains ester group, amide group and hydroxyl group, as polyethylene terephthalate, nylon and polycarbonate etc.Can carry out the even component reaction after adding this chainextender, the molar mass of increase material reaches chain extension, tackify and improves the purpose of material property.
Background technology
The high polymer material that contains ester agent, amide group and oh group, for example nylon (PA), polycarbonate (PC) and polyethylene terephthalate (PET) etc., mixing, extrude, in the processing of operation such as injection moulding, because the effect of heat, oxygen, aqueous vapor medium, can produce macromolecules degradation, cause the decline of material property, in addition serious in the degree that can not re-use.How to improve or to recover the performance of the macromolecular material of degraded to greatest extent, become one of key areas of research.Many units carried out the research of chainextender, but technological achievement and patent and few really realize commercial few especially.
Report according to " scientific and technological achievement information " second phase calendar year 2001, Beijing University of Chemical Technology is under the subsidy of the Ministry of Chemical Industry, nylon resin chainextender and chain extension technology have been researched and developed, polyfunctional compound with Heat stability is good is a chainextender, make the reaction of macromole generation even component improve the molecular weight of polymkeric substance, the physical and mechanical properties of nylon products is increased substantially.Chain extending reaction is finished with reactive extrusion technology usually, and the data that obtain are as follows:
| The resin title | Relative viscosity before the chain extension | Relative viscosity behind the chain extension |
| Nylon 6 | 2.2-2.4 | 2.9-6.0 |
| Nylon 66 | 2.2-2.4 | 2.9-5.3 |
| Waste nylon 66 | 2.6 | 3.1-4.2 |
This technology is just delivered as novel process, new technology, does not apply for a patent.Do not report the physical and mechanical properties index of PA product behind the concrete chain extension yet.
The country that East China University of Science bears " 863 " project---PET plastics recovery, the expert who has passed through the Department of Science and Technology checks and accepts.This technology adopts processing of low temperature solid phase and reactive extrusion technology, adds other auxiliary agents such as toughness reinforcing rubber, chainextender, makes the PET/PC alloy become a kind of high-performance, the good novel high polymer alloy material of application prospect.It is reported that comment of experts thinks that the preparation of this type material is two innovations greatly of the regeneration of polymeric scrap material and plastics secondary processing technology.
Do not find concrete data and whether applied for patent.Clearly the toughening effect of material is realized by elastomericss such as back adding rubber.Also not seeing provides the specific performance index.
Introduced the response type auxiliary agent CESA-Extend of Clariant (Clariant) masterbatch company in the SPE meeting in 2003, act as and make PET molecule long chain branching, do not needed just can improve the limiting viscosity that reclaims PET through the reactor solid state reaction.After adding the CESA-Extend chainextender, the PET molecular weight rises to the suitable molecular weight of new PET resin, does not reduce mechanical property, thermal characteristics and crystallinity simultaneously.Add CESA-Extend by twin screw extruder, PET need not give drying under high vacuum, only produce a spot of gel.Its another effect and advantage are the consistencies when improve reclaiming PET and other polyester, polycarbonate and nylon compounding.The patented technology that this additive is the specific function acrylated oligomer that provides of U.S. Johson polymkeric substance LLC company and Clariant owns this product together.The effective constituent that information announcing CESA-Extend is arranged is epoxy functionalized styrene/acrylic acid co-polymer.It is reported CESA-Extend can with blend polymer generation polycondensations such as PC, PA, POM, TPU and PBT, but to be used for PET the most effective, it is the poorest to be used for the nylon effect.The group that can react with it comprises amide group, isocyanate group, carboxylic acid ester groups and hydroxyl.
CESA-Extend improves the melt strength that reclaims the PET resin, be enough to satisfy the extrusion-blown modling of PET even reach the requirement of extruding blowing mould technology, limiting viscosity is after the CESA-Extend reaction of 0.75 not dried recovered PET and 3% is extruded, limiting viscosity rises to 0.78, and do not vacuumize equally with identical initial resin and expressing technique condition under, the recovery PET limiting viscosity that does not add chainextender reduces to 0.543.Limiting viscosity 0.558 recovery PET adds 2%CESA-Extend limiting viscosity after twin screw is extruded and rises to 0.673, if add 3%, then can rise to 0.720.
U.S.'s village minister (johnson) polymkeric substance company limited is an ADR-series at the product grade that China releases, sell at home, result of use is good, and the subject matter that reflects is to strengthen, fill regenerated engineering DeGrain, especially modified nylon aspect.But do not see actual result of use written report.
Sinopec Ba Ling branch office has synthesized a kind of glycidyl acrylate multipolymer in the laboratory.This multipolymer can make the tensile strength of PA6/PP0 alloy and elongation at break all be improved effectively.Present technique only is the paper report.
The multipolymer that University Of Science and Technology Of Tianjin uses polystyrene and acrylate to use emulsion polymerization to make is used as response type paper Wet Strength Resin.This test has only been delivered the paper report and has not been seen the result of use report.
Can analyze from above-mentioned data, research and commercially available chainextender all are to have two or more multi-functional groups to be polymerized, and the polymerization process of use has different, synthesis technique more complicated with the material of selecting for use more, and application surface is more single.Remove U.S.'s village minister (johnson) polymkeric substance company limited, the domestic material that works out does not only form product, and is only limited to a certain field, is unfavorable for very much promoting; Next is to use this chainextender, tensile strength, the flexural strength of raising resin that can be by a relatively large margin, but it is not obvious to improve the shock strength of material, and particularly reclaiming the macromolecular material shock strength low is a very important critical defect.
Summary of the invention
The objective of the invention is that a kind of technology that provides is simple, application surface is wide, improve processed-type, can improve chainextender of shock strength and preparation method thereof in the tensile strength that improves material, flexural strength in order to overcome the defective that above-mentioned prior art exists.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of macromolecule material chain extender is characterized in that, the composition of raw materials of this chainextender comprises:
| Component | Weight part |
| Styrene monomer | 50-75 |
| Vinylformic acid glyceride type monomer | 50-25 |
| Initiator | 0.0-1.2 |
| Dispersion agent | 0.1-1.0 |
| Auxiliary agent | 0.01-0.15 |
Described styrene monomer comprises vinylbenzene.
Described acrylic monomer comprises glycidyl methacrylate (ether).
Described initiator comprises peroxide initiator.
Described dispersion agent comprised polyvinyl alcohol, trimagnesium phosphate.
A kind of preparation method of chainextender is characterized in that, this method may further comprise the steps: select styrene monomer 50-75, vinylformic acid glyceride type monomer 50-25, initiator 0.1-1.2, dispersion agent 0.1-1.0, other auxiliary agent 0.01-0.15; Dispersion agent added in the suspension stir, initiator is dissolved in the monomer of styrenic and then adds vinylformic acid glyceride type monomer, under certain temperature and stirring velocity, aggregate into product until dissolving fully or mixing.
Compare with prior art, characteristics of the present invention are, the product that present technique is produced is the multipolymer that contains active epoxy group, with contain the ester agent, the high polymer material of amide group and oh group, nylon (PA) for example, polycarbonate (PC) and polyethylene terephthalate (PET) etc., mixing, extrude, injection moulding, carry out the even component reaction in the processing such as blowing and increase molar mass, improve processibility, improve the performance of material, but also can with the olefin type elastomer reaction that adds in the blend, make itself and macromolecular material effectively in conjunction with the impelling strength that improves system material.This is that above-mentioned technology is unexistent.
Compared with prior art, the present invention has characteristics such as technology is simple, relative molecular weight is higher, aftertreatment is easy, safe and reliable.
Embodiment
Below in conjunction with specific embodiment method involved in the present invention and technology are described,
Embodiment 1
(1) prescription
| Component | Weight part |
| Vinylbenzene | 75 |
| Glycidyl methacrylate | 25 |
| Dibenzoyl peroxide | 0.5 |
| Polyvinyl alcohol | 0.6 |
| The methyne orchid | In right amount |
(2) polymerization technique
1. in the 1000ml there-necked flask, add the 450ml ionized water, be warming up to 85-90 ℃, add the 0.6g polyvinyl alcohol, start and stir, dissolve fully up to dispersion agent;
2. component takes by weighing styrene monomer 75g and glycidyl methacrylate monomer 25g; Take by weighing the 0.5g dibenzoyl peroxide, it is dissolved in the vinylbenzene, and then add glycidyl methacrylate, mix the back and add there-necked flask;
3. control reaction temperature is noted keeping stirring velocity, prevents the polymer beads adhesion, according to graininess, and reaction 7-10h.Reaction process if find that excessive emulsion is arranged, can add micro-methyne orchid.
4. stop to stir, polymer beads is filtered collect,, remove the dispersion agent and the monomer of surface attachment with thermion water thorough washing.
5. oven dry back bottling preservation, stand-by.
(3) conversion unit
The Routine Test Lab polymerization equipment.
Embodiment 2
(1) prescription
| Component | Weight part |
| Vinylbenzene | 50 |
| Glycidyl methacrylate | 50 |
| Peroxy dicarbonate diisopropyl fat | 0.5 |
| Trimagnesium phosphate | 0.5 |
| The methyne orchid | In right amount |
(2) polymerization technique
6. in the 1000ml there-necked flask, add the 450ml ionized water, be warming up to 75-80 ℃, add the 0.5g trimagnesium phosphate, start and stir, up to being uniformly dispersed;
7. component takes by weighing styrene monomer 50g and glycidyl methacrylate monomer 50g; Take by weighing 0.5g peroxy dicarbonate diisopropyl fat, it is dissolved in the vinylbenzene, and then add glycidyl methacrylate, mix the back and add there-necked flask;
8. control reaction temperature is noted keeping stirring, and prevents the polymer beads adhesion, according to graininess, and reaction 7-10h.Reaction process if find that excessive emulsion is arranged, can add micro-methyne orchid.
9. stop to stir, polymer beads is filtered collect,, remove the dispersion agent and the monomer of surface attachment with thermion water thorough washing.
10. oven dry back bottling preservation, stand-by.
(3) conversion unit
The Routine Test Lab polymerization equipment.
Claims (5)
1. a chainextender is characterized in that, the composition of raw materials of this chainextender comprises:
2. according to a kind of chainextender under the claim 1, it is characterized in that described styrene monomer comprises vinylbenzene.
3. according to a kind of chainextender under the claim 1, it is characterized in that described acrylic monomer comprises glycidyl methacrylate (ether).
4. according to a kind of chainextender under the claim 1, it is characterized in that described initiator comprises peroxide initiator.
5. according to a kind of chainextender under the claim 1, it is characterized in that this method may further comprise the steps: select styrene monomer or polymkeric substance 50-75, vinylformic acid glyceride type monomer 50-25, initiator 0.1-1.2, dispersion agent 0.1-1.0, other auxiliary agent 0.1-0.3; Dispersion agent added in the suspension stir, initiator is dissolved in the monomer of styrenic and then adds vinylformic acid glyceride type monomer, under certain temperature and stirring velocity, carry out polymerization until dissolving fully or stirring.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101404099A CN101157739A (en) | 2006-10-08 | 2006-10-08 | Method for preparing macromolecule material chain extender |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101404099A CN101157739A (en) | 2006-10-08 | 2006-10-08 | Method for preparing macromolecule material chain extender |
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| CN101157739A true CN101157739A (en) | 2008-04-09 |
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| CNA2006101404099A Pending CN101157739A (en) | 2006-10-08 | 2006-10-08 | Method for preparing macromolecule material chain extender |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030861A (en) * | 2010-11-09 | 2011-04-27 | 长春工业大学 | Method for preparing epoxy functional acrylate polymer |
| CN102344564A (en) * | 2011-07-15 | 2012-02-08 | 张家港柴能生物科技有限公司 | Chain extender for polyamide preparation through chain extending |
| CN102344565A (en) * | 2011-07-15 | 2012-02-08 | 张家港柴能生物科技有限公司 | Method for directly polymerizing polycaprolactam |
| CN102936307A (en) * | 2012-11-27 | 2013-02-20 | 山西省化工研究所 | Epoxy functionalized chain extender, and preparation method and application thereof |
| CN103540123A (en) * | 2013-10-22 | 2014-01-29 | 山西省化工研究所（有限公司） | Chain extender composition used for recycling nylon and preparation method thereof |
| WO2015100517A1 (en) * | 2013-12-31 | 2015-07-09 | 内蒙古蒙西高新技术集团有限公司 | Substance containing multiple epoxy functional groups, preparation method therefor, terpolymer of same, carbon dioxide and epoxy propane, and copolymerization method therefor |
| CN105837722A (en) * | 2016-06-20 | 2016-08-10 | 王金明 | Preparation method of hydrophilic capacity-increasing chain extender |
| CN105859975A (en) * | 2016-06-19 | 2016-08-17 | 王金明 | Preparation method of capacity-increasing chain extender with core-shell structure |
| CN105859939A (en) * | 2016-06-20 | 2016-08-17 | 王金明 | Preparation method of organic silicon capacity increasing chain extender |
| CN106065043A (en) * | 2016-07-28 | 2016-11-02 | 王金明 | A kind of preparation method of the Organic fluoride hydrophobic type chain extender containing ionic liquid |
| CN106188369A (en) * | 2016-07-28 | 2016-12-07 | 王金明 | A kind of preparation method of the chain-expanding agent containing organic fluorinated silicone |
| WO2017107584A1 (en) * | 2015-12-22 | 2017-06-29 | 广东生益科技股份有限公司 | Epoxy resin modified polystyrene resin, preparation method therefor, and uses thereof |
| CN111378258A (en) * | 2020-03-28 | 2020-07-07 | 上海铭澜化工有限公司 | Tackifier for recycling waste PET textiles and recycling method of waste PET textiles |
| WO2021208234A1 (en) * | 2020-04-17 | 2021-10-21 | 佳易容聚合物(上海)有限公司 | Solvent-free adhesion-promoting chain extender, preparation method therefor, and application thereof |
-
2006
- 2006-10-08 CN CNA2006101404099A patent/CN101157739A/en active Pending
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030861B (en) * | 2010-11-09 | 2012-12-05 | 长春工业大学 | Method for preparing epoxy functional acrylate polymer |
| CN102030861A (en) * | 2010-11-09 | 2011-04-27 | 长春工业大学 | Method for preparing epoxy functional acrylate polymer |
| CN102344564A (en) * | 2011-07-15 | 2012-02-08 | 张家港柴能生物科技有限公司 | Chain extender for polyamide preparation through chain extending |
| CN102344565A (en) * | 2011-07-15 | 2012-02-08 | 张家港柴能生物科技有限公司 | Method for directly polymerizing polycaprolactam |
| CN102936307B (en) * | 2012-11-27 | 2015-10-21 | 山西省化工研究所 | The preparation method of a kind of epoxy-functional chainextender, epoxy-functional chainextender and application thereof |
| CN102936307A (en) * | 2012-11-27 | 2013-02-20 | 山西省化工研究所 | Epoxy functionalized chain extender, and preparation method and application thereof |
| CN103540123B (en) * | 2013-10-22 | 2016-02-17 | 山西省化工研究所（有限公司） | A kind of for chain extender composition reclaiming nylon and preparation method thereof |
| CN103540123A (en) * | 2013-10-22 | 2014-01-29 | 山西省化工研究所（有限公司） | Chain extender composition used for recycling nylon and preparation method thereof |
| WO2015100517A1 (en) * | 2013-12-31 | 2015-07-09 | 内蒙古蒙西高新技术集团有限公司 | Substance containing multiple epoxy functional groups, preparation method therefor, terpolymer of same, carbon dioxide and epoxy propane, and copolymerization method therefor |
| WO2017107584A1 (en) * | 2015-12-22 | 2017-06-29 | 广东生益科技股份有限公司 | Epoxy resin modified polystyrene resin, preparation method therefor, and uses thereof |
| CN106905459A (en) * | 2015-12-22 | 2017-06-30 | 广东生益科技股份有限公司 | A kind of epoxy resin modification polystyrene resin, preparation method and its usage |
| CN105859975A (en) * | 2016-06-19 | 2016-08-17 | 王金明 | Preparation method of capacity-increasing chain extender with core-shell structure |
| CN105837722A (en) * | 2016-06-20 | 2016-08-10 | 王金明 | Preparation method of hydrophilic capacity-increasing chain extender |
| CN105859939A (en) * | 2016-06-20 | 2016-08-17 | 王金明 | Preparation method of organic silicon capacity increasing chain extender |
| CN106065043A (en) * | 2016-07-28 | 2016-11-02 | 王金明 | A kind of preparation method of the Organic fluoride hydrophobic type chain extender containing ionic liquid |
| CN106188369A (en) * | 2016-07-28 | 2016-12-07 | 王金明 | A kind of preparation method of the chain-expanding agent containing organic fluorinated silicone |
| CN111378258A (en) * | 2020-03-28 | 2020-07-07 | 上海铭澜化工有限公司 | Tackifier for recycling waste PET textiles and recycling method of waste PET textiles |
| WO2021208234A1 (en) * | 2020-04-17 | 2021-10-21 | 佳易容聚合物(上海)有限公司 | Solvent-free adhesion-promoting chain extender, preparation method therefor, and application thereof |
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