CN1631918A - Method for parallel aqueous suspension preparation of chlorinated polyethylene - Google Patents
Method for parallel aqueous suspension preparation of chlorinated polyethylene Download PDFInfo
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- CN1631918A CN1631918A CN 200410087663 CN200410087663A CN1631918A CN 1631918 A CN1631918 A CN 1631918A CN 200410087663 CN200410087663 CN 200410087663 CN 200410087663 A CN200410087663 A CN 200410087663A CN 1631918 A CN1631918 A CN 1631918A
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Abstract
A method to prepare chlorinated polyethylene parallelled water-phase suspension is disclosed. In accordance with polyethylene powder with high density an and B which are made by different technique, choose different initiator and emulsifier, use the corresponding parameters and parallelled water-phase suspension method, devide the production into two paralleled technical course an and B, generate materials an and B chlorinated polyethylene through emulsification, chlorination and deacidification and deal kalization by waterand drying, mix the two ones with a certain ratio and add chemical agents, after heating acquire the product of chlorinated polyethylene with average structure of inside issure, emulsification, chlorination and deacidification and process kalization with water content of 33-37%, tensile strength larger than 10MPa and elongation at break larger than 500. The product chlorinated polyethylene is for waterproof and plastic materials.
Description
Technical field
The invention belongs to a kind of preparation method of chlorinatedpolyethylene.Be to adopt the parallel aqueous suspension explained hereafter to have the method for the chlorinatedpolyethylene of even internal organizational structure and tensile strength specifically.
Background technology
In recent years, along with the continuous expansion of chemical building material industrial expansion and end-use, the demand of medium-to-high grade waterproof roll is significantly increased.But, since nineteen eighty-two strengthens this new variety appearance of chlorinated polyethylene rubber waterproof roll, owing to be not specifically designed to the chlorinatedpolyethylene material of producing chlorinated polyethylene waterproof roll, cause waterproof roll vertically, transverse tensile strength and elongation at break appearance be than big-difference, general longitudinal tensile strength is greater than 9MPa, and horizontal 5MPa only.Not only having influenced inner quality and range of application, also made relevant department when working out chlorinated polyethylene waterproof roll detection index, can only be standard value with the mean value of vertical, horizontal tensile strength.
The performance of chlorinated polyethylene waterproof roll and plastic material depends on the character of chlorinatedpolyethylene.The performance of chlorinatedpolyethylene is then determined by its interior molecules structure and state of aggregation fully.And the factor that influences the chlorinatedpolyethylene structure mainly contains raw material, chlorination method and three aspects of chlorinity.Therefore, according to its purposes difference, the method for solution also emphasizes particularly on different fields.The application documents of application number 02135472.3 disclose a kind of " method for preparing water-phase suspension of rubber-type chlorinated polyethylene ", produce the synthetic rubber special use owing to be mainly, and the problem of unresolved vertical, horizontal tensile strength and elongation at break uniformity.The application documents of application number 03137941.9 disclose the method that a kind of water float glass process prepares the high workability chlorinated polyethylene resin, and the one, the kind of unexposed dispersion agent, tensio-active agent and initiator is difficult to carry out; The 2nd, the cl content of finished product chlorinatedpolyethylene is too wide in range, is unsuitable for producing chlorinated polyethylene waterproof roll and plastic material.
Summary of the invention
It is reasonable to the objective of the invention is to aim to provide a kind of starting material compatibility, and parameter is chosen science, and technology and treatment process are simple, and can produce the method for the waterproof roll and the impact-resistant modified special-purpose chlorinatedpolyethylene of plastic material of vertical, horizontal performance uniformity.
It is vertically good than transverse tensile strength to have according to the high density polyethylene(HDPE) of solvent method production, the then horizontal characteristics higher of the high density polyethylene(HDPE) that slurry process is produced than longitudinal tensile strength, and aqueous suspension chlorination process can keep the advantage of material polyethylene primary characteristic, the present invention is divided into A with the raw material high-density polyethylene powder by the production technique difference, two kinds of B, correspondence is chosen different auxiliary agents, to produce the corresponding A of being divided into, two parallel technical process of B, promptly adopt parallel water phase suspension, pass through certain emulsification separately, chloridized and washing depickling, after dealkalize and the drying, obtain A, two kinds of material chlorinatedpolyethylenees of B.A, B material are mixed by a certain percentage, handle, can make required special-purpose chlorinatedpolyethylene finished product through the heating homogenizing.
Its concrete technical scheme may further comprise the steps successively:
1, in two chlorination reaction still A, B arranged side by side, respectively adds 3000 parts of water by weight, be warmed up to 65 ℃, after adding 5～7 parts of Disperser Polysodium Methacrylate respectively, adding emulsifying agent A1 in chlorination reaction still A～2 parts, adding emulsifying agent B1 in chlorination reaction still B～2 parts.
2, by weight under agitation condition: in chlorination reaction still A, add 450～550 parts of high-density polyethylene powder A and 1.5～2.5 parts of initiator As; In chlorination reaction still B, add 450～550 parts of high-density polyethylene powder B and 1.5～2.5 parts of initiator Bs.
3, airtight chlorination reaction still A, B are warming up to 75 ℃, divide respectively to feed 570～600 parts of chlorine by weight three times, and during logical chlorine: reactor A controlled temperature is 136～138 ℃, pressure 0.6～0.7MPa, 6～8 hours time; Chlorination reaction still B controlled temperature is 133～135 ℃, pressure 0.3～0.6MPa, 5～6 hours time.
4, chlorination reaction still A, B are cooled to below 70 ℃, will be separately resultant wash depickling respectively, in and still add the alkali neutralization, washing still washing dealkalize, centrifuge dewatering and drying bed drying obtain two kinds of material chlorinatedpolyethylene A and B.
5, the heating homogenizing is handled: material chlorinatedpolyethylene A, B are gone into the mixing of homogenizing still by the ratio of 6: 4 or 5: 5, add 0.7～1.3% calcium stearate additive by weight, be warming up to 125～140 ℃, homogenizing place 1.5～3 hours makes chlorinity at 33～37% special-purpose chlorinatedpolyethylene product.Its optimum addition and processing parameter are: calcium stearate 1%, 130～135 ℃ of homogenization temperatures, 2 hours homogenizing time.
In the technique scheme, said emulsifying agent A was the oxyethylene group Viscotrol C, and initiator A is a dibenzoyl peroxide, and high-density polyethylene powder A is the high density polyethylene(HDPE) that solvent method is produced, melting index MI (190 ℃, 5kg)=0.4～0.6g/min.Emulsifying agent B is a Diisopropyl azodicarboxylate, and initiator B is the peroxidation acid amides, and high-density polyethylene powder B is the high density polyethylene(HDPE) that slurry process is produced, melting index MI (190 ℃, 5kg)=0.3～0.4g/min.
By the chlorinatedpolyethylene of above-mentioned condition and explained hereafter, detect through sampling analysis, its internal organizational structure is even, and every performance index are stable, realized purpose requirement of the present invention.
Leading indicator is:
Cl content 33～37% residual crystallinity≤2.0%
Heat decomposition temperature＞170 ℃ fugitive constituent≤0.2%
Transverse tensile strength 〉=10MPa longitudinal tensile strength 〉=10MPa
Transverse breakage elongation＞500 longitudinal fracture elongation＞500
Description of drawings
Accompanying drawing is the process flow diagram of method for parallel aqueous suspension preparation of chlorinated polyethylene of the present invention.
Flow process A is that starting material are high-density polyethylene powder A and auxiliary agent A, the technical process of production material chlorinatedpolyethylene A.
Flow process B is the technological process of production of material chlorinatedpolyethylene B.
Embodiment
Embodiment 1: the special-purpose production of chlorinated polyethylene technology of waterproof roll
1, emulsification, chlorination
Flow process A:
Be ready to starting material, various auxiliary agent, additive.
Raw material: high-density polyethylene powder A
Auxiliary agent: dispersion agent one sodium polymethacrylate
Initiator A-dibenzoyl peroxide
Emulsifying agent A-mistake oxyethylene group Viscotrol C
Additive: calcium stearate
Add 3000kg water in 5000 liters of reactors, constant temperature after unlatching is heated with stirring to 65 ℃ adds dispersion agent 6kg again, emulsifying agent A1.5kg, and high-density polyethylene powder A500kg, emulsification adds initiator A 2kg after 45 minutes, close manhole.Evacuate air heat temperature raising to 75 ℃ before the reaction.Divide three sections to feed 570kg chlorine, the entire reaction time is 7 hours, pressure 0.7MPa, temperature automatically controlled 137 ℃.Be cooled to after the reaction below 70 ℃, material is entered the washing still.
Flow process B:
Be ready to starting material, auxiliary agent, additive
Raw material: high-density polyethylene powder B
Auxiliary agent: dispersion agent-polymethyl acrylic acid is received
Initiator B-Diisopropyl azodicarboxylate
Emulsifying agent B-peroxidation acid amides
Additive: calcium stearate
Add 3000kg water in 5000 liters of reactors, constant temperature after unlatching is heated with stirring to 65 ℃ adds emulsifying agent B1.5kg, high-density polyethylene powder B500kg, and dispersion agent 6kg, emulsification adds initiator B 2kg after 45 minutes, close manhole.Evacuate air and heat temperature raising to 75 ℃ before the reaction divide three sections feeding 570kg chlorine, reacted 5 hours, and pressure 0.4MPa, 134 ℃ of temperature, temperature automatically controlled.When being cooled to below 70 ℃ after the reaction, material is entered the washing still.
2, washing
It is apparent neutral to the PH test paper that water cleans depickling in the washing still;
During the depickling material is pressed into and still, intensification limit, limit adds alkali, be warming up to 80 ℃ after insulation.Add alkali number control pH value between 6～8, be incubated 5 hours, the dry back of sampling shows neutral with the test paper test, and neutralization is finished;
When being cooled to below 60 ℃, will in and the still material be pressed into washing still dealkalize, water cleans material and reaches neutral, the material temperature is near cold water temperature;
Material is put into whizzer, separate moisture.
3, drying
Drying bed is warming up to 90 ℃ of insulations, and the wet feed after separating was added the drying bed inner drying 60 minutes, and the material fugitive constituent is that drying is finished below 0.3% after testing, is cooled to below 50 ℃.
4, the heating homogenizing is handled
To mix in the homogenizing still in 6: 4 ratio in material chlorinatedpolyethylene A, the B that flow process A and flow process B produce, add 1% calcium stearate additive, be warming up to 135 ℃, homogenizing after 2 hours after testing the qualified after-filtration of fugitive constituent, weigh, pack.
5. sampling analysis
The finished product leading indicator:
Cl content 36.2% residual crystallinity 1.8%
Transverse tensile strength 10.8MPa longitudinal tensile strength 10.9MPa
Transverse breakage elongation 520 longitudinal fracture elongations 560
Fugitive constituent 0.2%
Embodiment 2: the impact-resistant modified special-purpose production of chlorinated polyethylene technology of plastic material
1, emulsification, chlorination
Flow process A:
Be ready to starting material, various auxiliary agent, additive
Raw material: high-density polyethylene powder A
Auxiliary agent: dispersion agent-sodium polymethacrylate
Initiator A-dibenzoyl peroxide
Emulsifying agent A-mistake oxyethylene group Viscotrol C
Additive: calcium stearate
Add 3300kg water in 5000 liters of reactors, constant temperature after unlatching is heated with stirring to 65 ℃ adds dispersion agent 6.5kg, emulsifying agent A1.4kg, and high-density polyethylene powder A500kg, emulsification adds initiator A 2.2kg after 45 minutes, close manhole.Evacuate air before the reaction, heat temperature raising to 75 ℃.Divide three sections to feed 570kg chlorine, reacted pressure 0.5MPa, 134 ℃ of temperature 6 hours.Be cooled to after the reaction below 70 ℃, material is entered the washing still.
Flow process B:
Be ready to starting material, auxiliary agent, additive
Raw material: high-density polyethylene powder B
Auxiliary agent: dispersion agent-poly-methyl-prop diluted acid sodium
Initiator B-Diisopropyl azodicarboxylate
Emulsifying agent B-peroxidation acid amides
Additive: calcium stearate
Add 3300kg water in 5000 liters of reactors, unlatching is heated to 65 ℃ of constant temperature after stirring, and adds emulsifying agent B1.4kg, high-density polyethylene powder B500kg, and dispersion agent 6.5kg, emulsification adds initiator B 2.2kg after 45 minutes.Close manhole, evacuate air and heat temperature raising to 75 ℃.Divide three sections to feed 570kg chlorine, reacted 4 hours, pressure 0.4MPa, 130 ℃ of temperature, temperature automatically controlled.When being cooled to below 70 ℃ after the reaction, material is entered the washing still.
2, washing
It is apparent neutral to the PH test paper that water cleans depickling in the washing still.
During the depickling material is pressed into and still, intensification limit, limit adds alkali, adds alkali number control pH value between 6-8, be warming up to 80 ℃ after insulation 5 hours, the dry back of sampling shows neutral with the test paper test, neutralization is finished.
Be cooled to below 60 ℃, material is pressed into the dealkalize of washing still, water cleans material and reaches neutral, and temperature of charge is near cold water temperature.
Material is put into whizzer, separate moisture.
3, drying
Drying bed is warming up to 85 ℃ of insulations, and the wet feed after separating was added the drying bed inner drying 60 minutes, and the material fugitive constituent is that drying process is finished below 0.3% after testing, cools the temperature to below 50 ℃.
4, the heating homogenizing is handled
The material chlorinatedpolyethylene that to produce by flow process A and flow process B mixes in the homogenizing still in 5: 5 ratios, adds 1% calcium stearate additive, is warming up to 135 ℃, homogenizing after 2 hours after testing the qualified after-filtration of volatile content, weigh, pack.
5, sampling analysis
The finished product leading indicator:
Cl content 35.6% residual crystallinity 1.8%
172 ℃ of fugitive constituents 0.15% of heat decomposition temperature
Transverse tensile strength 11MPa longitudinal tensile strength 10.8MPa
Transverse breakage elongation 510 longitudinal fracture elongations 560
Claims (4)
1, a kind of method for parallel aqueous suspension preparation of chlorinated polyethylene is characterized in that in turn including the following steps:
A, in two chlorination reaction still A, B arranged side by side, respectively add 3000 parts of water by weight, be warmed up to 65 ℃, after adding 5～7 parts of Disperser Polysodium Methacrylate respectively, adding emulsifying agent A1 in chlorination reaction still A～2 parts, adding emulsifying agent B1 in chlorination reaction still B～2 parts;
B, by weight under agitation condition: in chlorination reaction still A, add 450～550 parts of high-density polyethylene powder A and 1.5～2.5 parts of initiator As; In chlorination reaction still B, add 450～550 parts of high-density polyethylene powder B and 1.5～2.5 parts of initiator Bs;
C, airtight chlorination reaction still A, B are warming up to 75 ℃, divide respectively to feed 570～600 parts of chlorine by weight three times, and during logical chlorine: chlorination reaction still A controlled temperature is 136～138 ℃, pressure 0.6～0.7MPa, 6～8 hours time; Chlorination reaction still B controlled temperature is 133～135 ℃, pressure 0.3～0.6MPa, 5～6 hours time;
D, chlorination reaction still A, B are cooled to below 70 ℃, will be separately resultant wash respectively depickling, in and still add alkali neutralization, the washing of washing still dealkalize, centrifuge dewatering and drying bed drying, obtain two kinds of material chlorinatedpolyethylene A and B;
E, heating homogenizing are handled: material chlorinatedpolyethylene A, B are gone into the mixing of homogenizing still by the ratio of 6: 4 or 5: 5, add 0.7～1.3% calcium stearate additive by weight, be warming up to 125～140 ℃, homogenizing was handled 1.5～3 hours, made chlorinity at 33～37% special-purpose chlorinatedpolyethylene product.
2, method for parallel aqueous suspension preparation of chlorinated polyethylene according to claim 1, it is characterized in that described emulsifying agent A was the oxyethylene group castor oil, initiator A is a dibenzoyl peroxide, high-density polyethylene powder A is the high density polyethylene(HDPE) that solvent method is produced, melting index MI (190 ℃, 5Kg)=0.4～0.6g/min.
3, method for parallel aqueous suspension preparation of chlorinated polyethylene according to claim 1, it is characterized in that described emulsifying agent B is a Diisopropyl azodicarboxylate, initiator B is the peroxidation acid amides, high-density polyethylene powder B is the high density polyethylene(HDPE) that slurry process is produced, melting index MI (190 ℃, 5Kg)=0.3～0.4g/min.
4, method for parallel aqueous suspension preparation of chlorinated polyethylene according to claim 1 is characterized in that described calcium stearate additive capacity is 1% by weight, and homogenization temperature is preferably in 130～135 ℃, preferably 2 hours homogenizing time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 200410087663 CN1281640C (en) | 2004-11-23 | 2004-11-23 | Method for parallel aqueous suspension preparation of chlorinated polyethylene |
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| CN 200410087663 CN1281640C (en) | 2004-11-23 | 2004-11-23 | Method for parallel aqueous suspension preparation of chlorinated polyethylene |
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| CN1631918A true CN1631918A (en) | 2005-06-29 |
| CN1281640C CN1281640C (en) | 2006-10-25 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100372874C (en) * | 2006-02-21 | 2008-03-05 | 赵东日 | Chlorinated polyethylene with high maximum elongation, and preparation process and application thereof |
| CN101704911B (en) * | 2009-11-14 | 2012-05-23 | 潍坊高信化工科技有限公司 | Method for producing highly-chlorinated polyethylene |
| CN102627811A (en) * | 2012-04-17 | 2012-08-08 | 哈尔滨中大型材科技股份有限公司 | Chlorinated polyethylene modified material for ultralow-temperature-resistance and high-toughness plastic and preparation method thereof |
| CN102924632A (en) * | 2012-11-27 | 2013-02-13 | 山东旭业新材料股份有限公司 | Double-component composite initiator and process for producing chlorinated polyethylene rubber material by virtue of double-component composite initiator |
| CN103304710A (en) * | 2013-06-27 | 2013-09-18 | 江苏中煦高分子材料有限公司 | Chlorinated metallocene polyethylene rubber |
| CN104250314A (en) * | 2014-02-25 | 2014-12-31 | 江苏煦和新材料有限公司 | Process for synthesis of high chlorinated medium viscosity metallocene polyethylene by aqueous phase suspension method |
| CN104829755A (en) * | 2015-05-13 | 2015-08-12 | 邵显清 | Water-phase suspension preparation method for hard chlorinated polyethylene |
| CN105504108A (en) * | 2016-01-05 | 2016-04-20 | 临沂奥星化工有限公司 | Preparation method for high-chlorinated polyethylene |
-
2004
- 2004-11-23 CN CN 200410087663 patent/CN1281640C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100372874C (en) * | 2006-02-21 | 2008-03-05 | 赵东日 | Chlorinated polyethylene with high maximum elongation, and preparation process and application thereof |
| CN101704911B (en) * | 2009-11-14 | 2012-05-23 | 潍坊高信化工科技有限公司 | Method for producing highly-chlorinated polyethylene |
| CN102627811A (en) * | 2012-04-17 | 2012-08-08 | 哈尔滨中大型材科技股份有限公司 | Chlorinated polyethylene modified material for ultralow-temperature-resistance and high-toughness plastic and preparation method thereof |
| CN102627811B (en) * | 2012-04-17 | 2016-08-03 | 哈尔滨中大型材科技股份有限公司 | Resistance to ultralow temperature, plastics chlorinated polyethylene modified material and the preparation method of high tenacity |
| CN102924632A (en) * | 2012-11-27 | 2013-02-13 | 山东旭业新材料股份有限公司 | Double-component composite initiator and process for producing chlorinated polyethylene rubber material by virtue of double-component composite initiator |
| CN103304710A (en) * | 2013-06-27 | 2013-09-18 | 江苏中煦高分子材料有限公司 | Chlorinated metallocene polyethylene rubber |
| CN103304710B (en) * | 2013-06-27 | 2015-05-27 | 江苏中煦高分子材料有限公司 | Chlorinated metallocene polyethylene rubber |
| CN104250314A (en) * | 2014-02-25 | 2014-12-31 | 江苏煦和新材料有限公司 | Process for synthesis of high chlorinated medium viscosity metallocene polyethylene by aqueous phase suspension method |
| CN104250314B (en) * | 2014-02-25 | 2017-11-14 | 江苏煦和新材料有限公司 | Viscosity metallocene PE synthesis technique in the high chlorination of water phase suspension |
| CN104829755A (en) * | 2015-05-13 | 2015-08-12 | 邵显清 | Water-phase suspension preparation method for hard chlorinated polyethylene |
| CN105504108A (en) * | 2016-01-05 | 2016-04-20 | 临沂奥星化工有限公司 | Preparation method for high-chlorinated polyethylene |
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| CN1281640C (en) | 2006-10-25 |
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