CN104292391A - Melting production method for unsaturated anhydride grafted chlorinated polyethylene - Google Patents
Melting production method for unsaturated anhydride grafted chlorinated polyethylene Download PDFInfo
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- CN104292391A CN104292391A CN201410049265.0A CN201410049265A CN104292391A CN 104292391 A CN104292391 A CN 104292391A CN 201410049265 A CN201410049265 A CN 201410049265A CN 104292391 A CN104292391 A CN 104292391A
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- chlorinated polyethylene
- carboxylic acid
- anhydride
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Abstract
The invention provides a melting production method for unsaturated anhydride grafted chlorinated polyethylene. The melting production method is characterized in that modified chlorinated polyethylene is produced by using a radical initiator, unsaturated carboxylic acid anhydride as a grafting agent and through the steps of mixing the initiator, unsaturated carboxylic acid anhydride and chlorinated polyethylene according to proportions, adding the mixture to a twin-screw extruder; carrying out one-step melt extrusion to graft chlorinated polyethylene with carboxylic acids. The modified chlorinated polyethylene is formed by optimal cooperation and extrusion processing of the following the components by mass: 100 parts of chlorinated polyethylene, 1-20 parts of unsaturated carboxylic acid anhydride and 0.8-10 parts of the radical initiator. The product has the advantages of excellent sulfuration manufacturability, physical and mechanical properties and compatibility. A typical flat region appears during sulfuration processing; tensile strength reaches 16.7 MPa; elongation at break reaches 446%; and the unsaturated anhydride grafted chlorinated polyethylene has relatively good blending property with non-polar polyethylene. The product/material is suitable for products such as automobile parts, acid resistant/oil resistant rubber tubes, wires and cables, sponge, sealing elements, waterproof coiled materials and flame-retardant rubber.
Description
Technical field
The present invention relates to a kind of unsaturated acid anhydride graft CPE melt production method.That is, with free agent initiator, unsaturated carboxylic acid anhydrides is grafting agent, add after being mixed in proportion with chlorinatedpolyethylene in twin screw extruder, melt extruded (extrusion reaction method) by a step, make chlorinated polyethylene grafting carboxylic acid, the chlorinatedpolyethylene of production graft modification.
This product/material is applicable to the goods such as auto parts machinery, acidproof/oil resisting rubber hose, electric wire, sponge, sealing member, waterproof roll and flame retardant rubber.
Background technology
Rubber-type chlorinated polyethylene (CM) has excellent weather-proof, resistance to ozone, chemical-resistant resistance, heat-resistant aging and a series of good characteristic such as fire-retardant, and its rich raw material sources, manufacturing process are simple, with low cost simultaneously.Therefore, CM and goods thereof are widely used in auto parts machinery, acidproof/oil resisting rubber hose, electric wire, sponge, sealing member, waterproof roll and anti-flaming rubber product, become the focus of research both at home and abroad.
But hinder the bottleneck of its large-scale application to be that consistency/autohension (with other material and poor by property) and sulfuration process bad (not having the smooth phase) and intensity are not high, therefore by modification and with etc. technology improve its performance and become critical problem.
2009, the people such as Chen Erfan report the CM by different model and use, thiourea curing system is adopted to successfully solve the bad problem of sulfuration process " also using of rubber-type chlorinated polyethylene " (China Synthetic Rubber Industry, 2009,32 (1): 58 ~ 61).
1994, the people such as Sun Yun C disclose " for improving the impact property of PVC and modification CPE " (US 5338803), it is grafting agent with nonsaturation vinyl monomer, as: methyl methacrylate etc., be initiator with organo-peroxide, adopt suspension polymerization to prepare graft CPE.
2006, Zhao Dong discloses " graft copolymer of chlorinated polyethylene-alkyl-acrylates and method for making and application " thereof (ZL 200610001895.6), it to account for the alkyl-acrylates compound of 5 25% and the chlorinatedpolyethylene of 75 95% puts into reactor, and add the tensio-active agent of water and 0.1 2%, stir in a nitrogen atmosphere and be warming up to 70 9 (TC, keep 0.5 2 hours, then the radical initiator adding 0.1 2% causes copolyreaction, and react 35 hours under the stirring velocity of 50 500 revs/min, obtain graft copolymer of chlorinated polyethylene-alkyl-acrylates.
2013, the people such as Tao Yong disclose " chlorinatedpolyethylene of chemical modification and the rubber combination of unsaturated rubber and preparation method thereof " (CN201310187446.5), the organic solvent of 600 parts, the chlorinatedpolyethylene of 60 parts are put into reactor by it, in 50 ° of C thermostatically heating baths, Keep agitation is until chlorinatedpolyethylene powder is in a solvent dispersed, then by the N of 2 weight parts, N-Thiocarb is dissolved in the dimethyl formamide of 50 weight parts, be added dropwise in reactor in 30 minutes, then Keep agitation heats 24 hours.Being poured into by reaction mixture in 1000 weight fraction distilled water makes the chlorinatedpolyethylene of replacement be precipitated out, then takes turns to embathe 3 times with alcohol, distilled water, and products therefrom is the chlorinatedpolyethylene of chemical modification.
Aforementioned production method can solve sulfuration process and the compatibility problem of chlorinatedpolyethylene, but it all comparatively bothers, and needs fairly large industrial production.
Summary of the invention
The object of the present invention is to provide a kind of unsaturated acid anhydride graft CPE melt production method.Relate to a kind of melt production method of rubber-type unsaturated acid anhydride graft CPE material, it is characterized in that: with free agent initiator, unsaturated carboxylic acid anhydrides is grafting agent, add after being mixed in proportion with chlorinatedpolyethylene in twin screw extruder, melt extruded (extrusion reaction method) by a step, make chlorinated polyethylene grafting carboxylic acid, the chlorinatedpolyethylene of production graft modification.
It is coordinated through optimizing by following composition by mass fraction, extrudes and process: chlorinatedpolyethylene consumption 100 parts; Unsaturated carboxylic acid anhydrides 1 ~ 20 part; Radical initiator 0.8 ~ 10 part.
Obtained unsaturated acid anhydride graft CPE has the advantages such as excellent sulfuration process, physical and mechanical properties and consistency (autohension).Sulfuration adds and has occurred typical plateau region man-hour, and tensile strength reaches 16.7MPa, and elongation at break reaches 446%, even the blended property better (consistency case) with nonpolar low density polyethylene (LDPE).
This product/material is applicable to the goods such as auto parts machinery, acidproof/oil resisting rubber hose, electric wire, sponge, sealing member, waterproof roll and flame retardant rubber.
The object of the invention is to be achieved through the following technical solutions:
Chlorinatedpolyethylene, unsaturated carboxylic acid anhydrides and radical initiator are joined in twin screw extruder in proportion successively, is melt extruded (extrusion reaction method) by a step, make chlorinated polyethylene grafting carboxylic acid, the chlorinatedpolyethylene of production graft modification.
After product is purified, after parking 10h, test percentage of grafting.
Then, the auxiliary agents such as the chlorinatedpolyethylene of modification, carbon black, process oil, anti-aging agent are joined in proportion successively in Banbury mixer after mixing, bottom sheet on a mill until, obtained performance test sample.Measure its sulfuration process, mechanical property.
Advantage of the present invention and effect are:
With radical initiator, unsaturated carboxylic acid anhydrides is grafting agent, makes chlorinated polyethylene grafting carboxylic acid, the chlorinatedpolyethylene of production graft modification by a step frit reaction method (extrusion reaction method).
1) radical initiator, unsaturated carboxylic acid anhydrides grafting agent is adopted, by the chlorinatedpolyethylene of a step frit reaction method production graft modification.
2) product sulfuration process is good, mechanical property is good, consistency (autohension) is good.
3) low production cost, is easy to the advantage such as industrialization and steady quality.
Accompanying drawing explanation
Fig. 1 be chlorinatedpolyethylene and maleic anhydride under the effect of BPO radical initiator, fusion-grafting is the reaction mechanism of chlorinatedpolyethylene-maleic anhydride grafts.
Fig. 2 is the vulcanization curve of 1. grafting CM and 2. non-grafting CM.Curing temperature 170 DEG C; Grafting CM: percentage of grafting 8%; MA 8 parts, BPO 3.2 parts.
Fig. 3 is grafting CM and LDPE(80/20) stereoscan photograph of blend sample: the blend of (a) non-grafting CM; The blend of (b) grafting CM.
Embodiment
Chlorinatedpolyethylene, unsaturated carboxylic acid anhydrides and radical initiator are joining in twin screw extruder by the present invention in proportion in proportion successively, melt extruded (extrusion reaction method) by a step, make chlorinated polyethylene grafting carboxylic acid, the chlorinatedpolyethylene product of obtained graft modification.
percentage of grafting measures:
Grafting samples is put into reactor, add dimethylbenzene 145 DEG C of reflux extraction 24h of 50 times, make it fully swelling, to remove unreacted grafted monomer and possible maleic anhydride polymer, then put into the dry 10h of vacuum drying oven for 80 DEG C, obtain the chlorinated polyethylene grafting thing of purifying.
Accurately take the grafting samples 0.2g of own purifying, put into Erlenmeyer flask, add 50ml dimethylbenzene, 145 DEG C of reflux lh, to swelling, instill excessive NaOH-ethanol 0.lmol/L standardized solution, then drip and take on a red color to solution into several phenolphthalein indicators time while hot, reheat 10min, excessive alkali HCI-Virahol standardized solution (0.lmol/L) is counter drop to colourless till, and do blank test, the calculation formula of percentage of grafting is as follows:
In formula: V
1for the volume of NaOH mono-ethanolic soln that titration adds;
V
2for the volume of HCI mono-aqueous isopropanol that titration consumes;
C
1for the volumetric molar concentration of NaOH mono-ethanolic soln;
C
2for the volumetric molar concentration of HCI mono-aqueous isopropanol;
W is the quality of the purifying grafts accurately taken;
M is the molar mass of maleic anhydride;
NaOH mono-ethanol standardized solution is 0.1mol/L;
HCI mono-Virahol standardized solution is 0.1mol/L, by GB/T264-1983 preparation and demarcation.
the preparation of rubber unvulcanizate:
The auxiliary agents such as the chlorinatedpolyethylene of modification, carbon black, process oil, anti-aging agent are joined in proportion successively in Banbury mixer after mixing, bottom sheet on a mill until, obtained performance test sample.Measure its sulfuration process, mechanical property etc.
performance test:
With vulcanization of rubber determinator GT-M2000-A(High Speed Rail Testing Instruments company limited) test the sulfuration process of grafting samples and non-grafting samples;
Tensile strength and elongation at break are tested according to GB/T528-2009, and carry out tension test at RGL-30A type (Shenzhen Rui Ge limited liability company) tensile testing machine to sample, rate of extension is 500mm/min;
Analysis of Surface Topography is carried out with scanning electron microscope sem (Japanese JSM-6360LV) the low-temperature brittle fracture face to the blended sample of CM/LDPE.
embodiment 1
Dried CM 100 mass parts and MA 8 parts and BPO 3.2 parts are joined in twin screw extruder successively and extrudes, prepared graft CPE sample.
After purification of samples parks 10h, test percentage of grafting is 8%.
Chlorinatedpolyethylene after modification purifying and the auxiliary agents such as carbon black, process oil, anti-aging agent are joined in proportion successively after mixing in Banbury mixer, bottom sheet on a mill until, the cross-linked rubber sample of obtained performance test.Measure its sulfuration process, mechanical property.
Vulcanization curve is shown in the curve 1 of Fig. 2; Tensile strength is 16.7MPa, and elongation at break reaches 446%, hardness Shao A65.
comparative example 1
With the CM of non-graft modification, by describing the cross-linked rubber sample preparing non-grafting CM in embodiment 1.Measure sulfuration process, mechanical property.
Vulcanization curve is shown in the curve 2 of Fig. 2; Tensile strength is 8.0MPa, and elongation at break reaches 427.7%, hardness Shao A63.
embodiment 2
Dried CM 100 mass parts and CTA 5 parts and CYHPO 0.8 part are joined in twin screw extruder successively and extrudes, prepared graft CPE sample.
By the CM cross-linked rubber sample describing preparation graft modification in embodiment 1.Tensile strength is 15.9MPa, and elongation at break reaches 436.3%, hardness Shao A61.
embodiment 3
Dried CM 100 mass parts and DMMA 30 parts and TBHP 10 parts are joined in twin screw extruder successively and extrudes, prepared graft CPE sample.
By the CM cross-linked rubber sample describing preparation graft modification in embodiment 1.Tensile strength is 19.9MPa, and elongation at break reaches 416.1%, hardness Shao A68.
embodiment 4
Dried CM 100 mass parts and ACA 15 parts and BPO 2.8 parts are joined in twin screw extruder successively and extrudes, prepared graft CPE sample.
By the CM cross-linked rubber sample describing preparation graft modification in embodiment 1.Tensile strength is 17.6MPa, and elongation at break reaches 426.8%, hardness Shao A66.
embodiment 5
Dried CM 100 mass parts and PMA 12 parts and AIBN 6 parts are joined in twin screw extruder successively and extrudes, prepared graft CPE sample.
By the CM cross-linked rubber sample describing preparation graft modification in embodiment 1.Tensile strength is 16.9MPa, and elongation at break reaches 417.8%, hardness Shao A66.
embodiment 6
Dried CM 100 mass parts and ITA 10 parts and ABVN 5 parts are joined in twin screw extruder successively and extrudes, prepared graft CPE sample.
By the CM cross-linked rubber sample describing preparation graft modification in embodiment 1.Tensile strength is 17.4MPa, and elongation at break reaches 416.9%, hardness Shao A67.
embodiment 7
Dried CM 100 mass parts and PA 5 parts and DCP 3.8 parts are joined in twin screw extruder successively and extrudes, prepared graft CPE sample.
By the CM cross-linked rubber sample describing preparation graft modification in embodiment 1.Tensile strength is 17.6MPa, and elongation at break reaches 441.1%, hardness Shao A65.
comparative example 2
After plasticating respectively with the CM of the graft modification of embodiment 1 and low density polyethylene (LDPE), prepare the rubber unvulcanizate test sample of graft modification CM and low density polyethylene (LDPE) by the rubber unvulcanizate preparation method described by embodiment 1.
Tensile strength is 18.2MPa, and elongation at break reaches 412.8, hardness Shao A72.
The performance of the sample in comparing embodiment and comparative example, can find out:
Graft modification CM product of the present invention all obviously improves than the sulfuration process of the CM sample of non-grafting, has occurred the typical smooth phase.
Graft modification CM product of the present invention all doubles above than the tensile strength of the CM sample of non-grafting, elongation at break and changes in hardness little.
Can find out from comparative example 2 and accompanying drawing 3, without the CM/PE blend of graft modification matrix between interface clear, be separated obviously, Fig. 3 (a).
And interface is fuzzyyer between the matrix of graft modification CM product of the present invention and low density polyethylene (LDPE) blend blend, Fig. 3 (b), i.e. Compatibility improvement, illustrate that graft modification CM of the present invention has good consistency or autohension.
Meanwhile, low cost of manufacture, the steady quality of product/material of the present invention.
On the other hand, the grafting adopted in the present invention completes in molten state, decreases the environmental pollution of solvent working system.Form new growth engines, the theory of be correlated with to material and goods and the development of production have reference function, improve the progress of polymer novel material industry, have impelled the update of rubber-plastics material and product, had important Social benefit and economic benefit.
Claims (6)
1. a unsaturated acid anhydride graft CPE melt production method, relate to a kind of melt production method of rubber-type unsaturated acid anhydride graft CPE material, it is characterized in that: with free agent initiator, unsaturated carboxylic acid anhydrides is grafting agent, add in proportion in forcing machine with chlorinatedpolyethylene, melt extruded (extrusion reaction method) by a step, make chlorinated polyethylene grafting carboxylic acid, the chlorinatedpolyethylene of production graft modification.
2. according to melt production method according to claim 1, it is characterized in that: chlorinatedpolyethylene, unsaturated carboxylic acid anhydrides and radical initiator are added in twin screw extruder in proportion, melt extrude (extrusion reaction method) by a step and make chlorinated polyethylene grafting carboxylic acid.
3. according to unsaturated carboxylic acid anhydrides according to claim 1, it is characterized in that: maleic anhydride (MA), citraconic anhydride (CTA), dimethyl maleate acid anhydride (DMMA), aconitic anhydride (ACA), phenylmaleic anhydride (PMA), itaconic anhydride (ITA), or Tetra hydro Phthalic anhydride (PA).
4. according to unsaturated carboxylic acid anhydrides according to claim 3, it with measure feature is: 5 ~ 30 parts (with chlorinatedpolyethylene 100 mass fraction for radix).
5. according to radical initiator according to claim 1, it is characterized in that: dibenzoyl peroxide (BPO), dicumyl peroxide (DCP), cyclohexanone peroxide (CYHPO), tertbutyl peroxide (TBHP), Diisopropyl azodicarboxylate (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN).
6. according to radical initiator according to claim 5, it with measure feature is: 0.8 ~ 10 part.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106592566A (en) * | 2016-11-25 | 2017-04-26 | 南京尔凡塑胶科技有限公司 | Honeycomb type plastic civil grille and production process thereof |
| CN110821046A (en) * | 2019-11-20 | 2020-02-21 | 北京市建筑工程研究院有限责任公司 | Slow-bonding prestressed tendon and preparation method thereof |
| CN112409542A (en) * | 2020-12-10 | 2021-02-26 | 潍坊硕邑化学有限公司 | Continuous reaction production method of maleic anhydride grafted chlorinated polyethylene copolymer rubber |
| CN114456319A (en) * | 2021-12-24 | 2022-05-10 | 潍坊亚星化学股份有限公司 | Maleic anhydride melt-grafted chlorinated polyethylene/polypropylene composite elastomer material and preparation method thereof |
| CN114957555A (en) * | 2022-04-21 | 2022-08-30 | 北京化工大学常州先进材料研究院 | Preparation method of modified chlorinated polyethylene |
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| CN102344615A (en) * | 2011-06-24 | 2012-02-08 | 四川明星电缆股份有限公司 | Cable sheath material |
| CN103361008A (en) * | 2012-04-02 | 2013-10-23 | 上海通悦包装材料有限公司 | Preparation method of hot melt adhesive composition |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101100497A (en) * | 2007-06-08 | 2008-01-09 | 深圳市科聚新材料有限公司 | All-purpose double-screw extruder one-time extracted graft and preparation method thereof |
| CN102344615A (en) * | 2011-06-24 | 2012-02-08 | 四川明星电缆股份有限公司 | Cable sheath material |
| CN103361008A (en) * | 2012-04-02 | 2013-10-23 | 上海通悦包装材料有限公司 | Preparation method of hot melt adhesive composition |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106592566A (en) * | 2016-11-25 | 2017-04-26 | 南京尔凡塑胶科技有限公司 | Honeycomb type plastic civil grille and production process thereof |
| CN106592566B (en) * | 2016-11-25 | 2018-10-23 | 南京尔凡塑胶科技有限公司 | Honeycomb type plastic civil grille and production process thereof |
| CN110821046A (en) * | 2019-11-20 | 2020-02-21 | 北京市建筑工程研究院有限责任公司 | Slow-bonding prestressed tendon and preparation method thereof |
| CN112409542A (en) * | 2020-12-10 | 2021-02-26 | 潍坊硕邑化学有限公司 | Continuous reaction production method of maleic anhydride grafted chlorinated polyethylene copolymer rubber |
| CN114456319A (en) * | 2021-12-24 | 2022-05-10 | 潍坊亚星化学股份有限公司 | Maleic anhydride melt-grafted chlorinated polyethylene/polypropylene composite elastomer material and preparation method thereof |
| CN114957555A (en) * | 2022-04-21 | 2022-08-30 | 北京化工大学常州先进材料研究院 | Preparation method of modified chlorinated polyethylene |
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Application publication date: 20150121 |