CN107573460A - A kind of organosilicon maleic anhydride resin new copolymer - Google Patents
A kind of organosilicon maleic anhydride resin new copolymer Download PDFInfo
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- CN107573460A CN107573460A CN201710593784.7A CN201710593784A CN107573460A CN 107573460 A CN107573460 A CN 107573460A CN 201710593784 A CN201710593784 A CN 201710593784A CN 107573460 A CN107573460 A CN 107573460A
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- maleic anhydride
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- peroxide
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Abstract
The invention provides a kind of organosilicon maleic anhydride resin copolymer and preparation method thereof.The copolymer be by（Weight %）Resin 10~98, vinyl organosilicon polymer 0.1~80, maleic anhydride or GMA 0.3~10, styrene or acrylate 0~50, initiator 0.01~5, aided initiating 0~3, it is polymerize in reactor or is process in double screw extruder through an extruding polymerization by certain proportioning.The copolymer of the present invention not only has polar functional group, can be used as modifying plastics compatilizer, improve the mechanical property of composite, and contains organosilicon polymer, can improve the advantages that composite material surface glossiness is good, suitable for manufacturing a variety of modified plastics.
Description
Technical field
The present invention relates to a kind of organosilicon maleic anhydride resin copolymer and preparation method thereof.
Background technology
For engineering plastics in the market mainly based on nylon resin and polyester resin, nylon resin mainly includes tree
Fat：Nylon 6 resin and nylon 66 resin, polyester resin mainly have polybutylene terephthalate (PBT)（PBT）, poly terephthalic acid
Glycol ester（PET）And makrolon（PC）.Engineering plastics product is widely used in communications and transportation, electronic apparatus, machinery zero
The fields such as part, electric tool, office accommodation, furniture part and assembly.PC toughness is preferable in these engineering plastics, other engineering plastics
It is required for adding elastomer progress toughness reinforcing when in use.
The elastic body active of toughness reinforcing engineering plastics will have ethylene-acrylate elastomer, ethylene-acrylic acid on the market at present
Ester-GMA ternary polymerization elastomer and the contracting of polyolefin elastomer grafted maleic anhydride or methacrylic acid
Water glyceride（GMA）.For elastomer because addition is smaller, to play toughening effect must fully dispersed into resin, above-mentioned bullet
Property body when in use there is being not easy the characteristics of scattered, in order to improve dispersion effect, in maleic anhydride or methyl-prop in the present invention
Olefin(e) acid ethylene oxidic ester can improve elastomer dispersion effect with introducing organosilicon polymer in resin copolymer, be filled for height
Fire-retardant reinforcing material can improve the smooth in appearance degree of material.
The content of the invention
Resin in the present invention includes polyethylene, polypropylene, polystyrene, high impact polystyrene, acrylic nitrile-butadiene two
Alkene-styrol copolymer, acrylonitritrile-styrene resin, ethylene vinyl acetate copolymer, ethene and octene elastomer, second
Alkene-amylene elastomer, ethylene-butylene elastomer, ethylene propylene diene rubber, EP rubbers, s-B-S rubber,
Hydrogenated styrene-butadiene-styrene rubber.These resins, which can be used alone to mix in proportion as needed, to be made
With.
Vinyl organosilicon polymer in the organosilicon maleic anhydride resin copolymer of the present invention is to contain vinyl silicon
Oil contains vinylsiloxane rubber, and both materials, which can be used alone, can also mix the effect for reaching different according to a certain percentage
Fruit.The contents of ethylene of vinyl silicone oil can be 0.01~6%, and molecular weight ranges are 1500~50000.Vinylsiloxane rubber
Contents of ethylene can be 0.01~5%, molecular weight ranges are 70000~500000.
Polar comonomers in the organosilicon maleic anhydride resin copolymer of the present invention are maleic anhydride or metering system
Acid glycidyl ester.It can polymerize in polymer containing maleic anhydride or GMA polar monomer with other
Terminal polar group group in thing is reacted, and the mechanical performance of blend can be improved as the compatilizer of different mixture thing.Such as
Fruit contains elastomer in the blend, then can improve the impact property of material.Can improve matrix with without the compatible of tassement polaire
Property, improve the mechanical performance of material.
Wherein initiator in the organosilicon maleic anhydride resin copolymer of the present invention is peroxide initiator, azo
Initiator and redox initiator.Peroxide has cyclohexanone peroxide, dibenzoyl peroxide, dilauroyl peroxide, different
Propyl group hydrogen peroxide, TBHP, potassium peroxydisulfate, ammonium persulfate, cumyl peroxide, di-t-butyl peroxide,
The mixture of peroxidized t-butyl perbenzoate and/or these compounds.Azo-initiator has azodiisobutyronitrile, azo two different
The mixture of heptonitrile and/or these compounds.Redox initiator is water soluble oxidized-reduction initiator or oil-soluble oxygen
Change-reduction initiator, mainly there are persulphate-bisulphite sodium, isopropyl benzene hydroperoxide-ferrous salt, hydrogen peroxide-ferrous iron
Salt, dibenzoyl peroxide-dimethylaniline, dibenzoyl peroxide-dimethyl toluidine, peroxide-metal alkyl（Three
Aluminium ethide, boron triethyl, lead diethide）Oxygen-metal alkyl etc..
Aided initiating in the organosilicon maleic anhydride resin copolymer of the present invention is iso-cyanuric acid triallyl ester, by
In there is three pi-allyls on iso-cyanuric acid triallyl ester, can preferentially with initiator caused by radical reaction, improve pole
The reaction probability of property monomer.
The present invention organosilicon maleic anhydride resin copolymer in preparation method be by certain proportioning in reactor
Be granulated after polymerization in double screw extruder or by certain proportioning in double screw extruder melting, be kneaded, extrusion, cooling, dry
Dry, pelletizing and packaging.
With traditional maleic anhydride or GMA compared with resin copolymer, of the invention has
Organosilicon polymer and maleic anhydride or GMA employ new polymerization system with resin copolymer, excellent
Changed processing characteristics, the organosilicon polymer and maleic anhydride or GMA of gained and resin copolymer with
In the market existing product compares the advantages of to have that polarity is strong, outward appearance is good, easy processing is scattered etc. a series of prominent, is very suitable for setting
Fat is modified, mineral-filled and material toughness reinforcing etc., has and very big applies future.
The present invention is shown in Table 1 by example below checking：
The present invention the specific operating procedure of organosilicon maleic anhydride resin copolymer embodiment be：
First by maleic anhydride or GMA and initiator cumyl peroxide in styrene or acrylic acid
Formicester dissolves in acetone, then with polyvinyl resin, vinyl silicone oil, aided initiating iso-cyanuric acid triallyl ester and
After other additives are sufficiently mixed under agitation, are melted, be kneaded by double screw extruder, extruded, cooled down, dried, pelletizing and
Packaging.Each zone temperature of barrel should be maintained between 170 °C~230 °C
Double screw extruder draw ratio applied to preparation method of the present invention is 36~60, and screw speed is 200~400 revs/min
Clock.
Copolymer prepared by each embodiment tests polar monomer content in following manner：
Maleic anhydride and the measure of GMA contents
1）Copolymer refines
About 4 grams of copolymers are weighed, adds in 250mL cucurbits and dissolves by heating together with 200mL dimethylbenzene, flow back 8~10h, cold
But acetone is added afterwards to shake, is filtered after staticly settling, then is washed with acetone, and filtrate is put into 90 DEG C of baking ovens and dries 10h, it is cold
It is stand-by.
2）The measure of maleic anhydride content
The copolymer that about 2g has been refined is weighed, about 80mL dimethylbenzene is added, is heated to reflux about 20min
To dissolving.Excessive KOH- ethanol standard liquids, then the 6h that flows back are added after cooling, using phenolphthalein as indicator after cooling,
With the excessive KOH- ethanol standard liquids of HCL- isopropanol standard liquids back titration, the horse calculated after blank value in copolymer is deducted
Carry out anhydride content.
3）The measure of GMA contents
The copolymer that about 1g has been refined is weighed, is dissolved in 100mL xylene solubles, adds a certain amount of trichloroacetic acid/toluene.Heating
Flow back about 60min.Room temperature is cooled to, adds appropriate phenolphthalein to be titrated as indicator with certain density KOH- methanol standard liquid
To terminal, the GMA contents in copolymer are calculated after deduction blank value.
Embodiment formula table and copolymer testing result are shown in Table 1
The embodiment formula table of table 1 and copolymer testing result
Claims (8)
1. the invention provides a kind of organosilicon maleic anhydride resin copolymer, its feature composition（Weight %）For：Resin 10~
98, vinyl organosilicon polymer 0.1~80, maleic anhydride or GMA 0.3~10, styrene or third
Olefin(e) acid ester 0~50, radical initiator 0.01~5, aided initiating 0~3.
A kind of 2. organosilicon maleic anhydride resin copolymer according to claim 1, wherein described resin includes poly- second
Alkene, polypropylene, polystyrene, high impact polystyrene, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene are common
Polymers, ethylene vinyl acetate copolymer, ethene and octene elastomer, ethylene-pentene elastomer, ethylene-butylene elastomer, three
First EP rubbers, EP rubbers, s-B-S rubber, hydrogenated styrene-butadiene-styrene rubber and/
Or the mixture of these compounds.
A kind of 3. organosilicon maleic anhydride resin copolymer according to claim 1, wherein described vinyl organosilicon
Polymer is the mixture of vinyl silicone oil, vinylsiloxane rubber and/or these compounds.
A kind of 4. organosilicon maleic anhydride resin copolymer according to claim 1, wherein described polar comonomers
For maleic anhydride or GMA.
A kind of 5. organosilicon maleic anhydride resin copolymer according to claim 1, wherein described styrene or propylene
Acid esters is styrene, a- methyl styrenes, acrylonitrile, methymethacrylate, methacrylate, ethyl acrylate, acrylic acid
Butyl ester, 2-ethyl hexyl acrylate.
6. a kind of organosilicon maleic anhydride resin copolymer according to claim 1, wherein initiator draw for peroxide
Send out agent, azo-initiator and redox initiator；Peroxide has cyclohexanone peroxide, dibenzoyl peroxide, peroxide
Change lauroyl, hyperis, TBHP, potassium peroxydisulfate, ammonium persulfate, cumyl peroxide, peroxide
Change the mixture of di-t-butyl, peroxidized t-butyl perbenzoate and/or these compounds；Azo-initiator has the isobutyl of azo two
The mixture of nitrile, ABVN and/or these compounds；Redox initiator is water soluble oxidized-reduction initiator
Or oil insoluble oxidation-reduction initiator.
A kind of 7. organosilicon maleic anhydride resin copolymer according to claim 1, wherein described aided initiating is three
Pi-allyl fulminuric acid ester.
8. a kind of organosilicon maleic anhydride resin copolymer according to claim 1, its preparation method are matched somebody with somebody by certain
Than in reactor polymerize after double screw extruder be granulated or by certain proportioning in double screw extruder through once extruding
Polymerization granulation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710593784.7A CN107573460A (en) | 2017-07-20 | 2017-07-20 | A kind of organosilicon maleic anhydride resin new copolymer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710593784.7A CN107573460A (en) | 2017-07-20 | 2017-07-20 | A kind of organosilicon maleic anhydride resin new copolymer |
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| CN107573460A true CN107573460A (en) | 2018-01-12 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116217834A (en) * | 2023-02-11 | 2023-06-06 | 江苏乐离新材料科技有限公司 | Preparation method of polyacrylate organosilicon modified water-soluble equipment protective film solution |
| CN118240290A (en) * | 2024-03-22 | 2024-06-25 | 广东金源塑胶科技有限公司 | High-strength and high-toughness antibacterial polyethylene plastic and preparation method thereof |
-
2017
- 2017-07-20 CN CN201710593784.7A patent/CN107573460A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116217834A (en) * | 2023-02-11 | 2023-06-06 | 江苏乐离新材料科技有限公司 | Preparation method of polyacrylate organosilicon modified water-soluble equipment protective film solution |
| CN118240290A (en) * | 2024-03-22 | 2024-06-25 | 广东金源塑胶科技有限公司 | High-strength and high-toughness antibacterial polyethylene plastic and preparation method thereof |
| CN118240290B (en) * | 2024-03-22 | 2024-08-23 | 广东金源塑胶科技有限公司 | High-strength and high-toughness antibacterial polyethylene plastic and preparation method thereof |
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Application publication date: 20180112 |