CN105837713A - Method for preparing high-insulating chlorinated polyethylene - Google Patents
Method for preparing high-insulating chlorinated polyethylene Download PDFInfo
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- CN105837713A CN105837713A CN201610372772.7A CN201610372772A CN105837713A CN 105837713 A CN105837713 A CN 105837713A CN 201610372772 A CN201610372772 A CN 201610372772A CN 105837713 A CN105837713 A CN 105837713A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
- C08F8/22—Halogenation by reaction with free halogens
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09J161/14—Modified phenol-aldehyde condensates
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Abstract
The invention provides a method for preparing high-insulating chlorinated polyethylene and belongs to the technical field of chlorinated polyethylene production. The method comprises the steps of chlorination, washing filtration, leaching, centrifugation and drying. The washing filtration means that a material having undergone the chlorination is cooled to below 95 DEG C and then transferred to a washing kettle and washed once with water, and the moisture is filtered out to obtain a washed material; the leaching means that the washed material is soaked with water in an acid-proof container and soaked for 3 h or above; the centrifugation means that an acid-proof centrifuge is adopted to remove moisture in the material having been soaked; and an acid-proof fluidized drying bed is adopted for drying. The obtained chlorinated polyethylene product has good insulativity, and the volume resistivity reaches 1015 omega.cm or above.
Description
[technical field]
The present invention relates to the production technical field of chlorinated polyethylene, be specifically related to the system of a kind of high-insulativity chlorinated polyethylene
Preparation Method.
[background technology]
Electric wire is general power transmission material, is in use required to have certain insulating properties.Electric wire electricity
The insulant that cable is conventional has thermoplastic elastomer (TPE) (TPE), polrvinyl chloride (PVC), Low Density Polyethylene (LDPE), crosslinking synthesis
Polymer (XL), chlorinated polyethylene (CPE) and ethylene propylene diene rubber etc..Wherein, chlorinated polyethylene (CPE) is by high-density polyethylene
The macromolecular material that alkene (HDPE) prepares through chlorination substitution reaction.
CPE has excellent weather resisteant, resistance to ozone, chemical-resistant resistance and ageing-resistant performance, and oil resistivity, fire resistance are good,
Can mixing, high comprehensive performance in varing proportions with other macromolecular materials such as PVC, PE and SR.It is used at chlorinated polyethylene
In electric wire aspect, in the early time in order to ensure the insulating properties of electric wire, many use ethylene propylene diene rubbers make, due to EPDM
Glue price is the highest, develops into later use chlorinated polyethylene rubber the most mixed with EPDM, how at formula body
In system, the more chlorinated polyethylene rubber using low price or use chlorinated polyethylene rubber completely are just to reduce holistic cost
Being a critically important subject under discussion, chlorinated polyethylene rubber ratio in formula is determined by its electrical insulation capability, electrical insulation capability
The best ratio just can the biggest replace the most completely.
The insulating properties of chlorinated polyethylene and its production technology have certain relation.Chlorinated polyethylene (CPE) produces work at present
Skill mainly has water phase suspension and acid phase suspension method, and traditional water phase suspension will be through the processes such as deacidification, neutralization, dealkalize, meeting
Bring more conductive ion, and these conductive ions cannot be removed completely, and electric property is had considerable influence.Use acid phase process
Production can reduce the content of charged ion, and the Chinese patent of Publication No. CN101831019A discloses one " high electricality
Can the preparation method of rubber-type chlorinated polyethylene ", the method uses acid phase suspension method to produce chlorinated polyethylene, and it passes through
When cleaning product use deionized water, improve the insulating properties of product to a certain extent, although but acid phase process do not have
The process neutralized, does not produce charged ion, but its process do not cleaned, soak, deacidification is thorough, has the performance of product
Harmful effect, product stores 3-6 month easily there is the problem that product turns to be yellow.
It addition, use acid phase suspension method to filter containing the concentration higher (about 28%) of acid, follow-up vacuum used due to product
The equipment such as machine, centrifuge, drying machine are required to use the extraordinary material of acid resistance to make, and investment cost is the highest, and the party
The material particle that method prepares is relatively thicker, needs to be ground it, needs to expend more electric energy, and it produces and to use specially in addition
Deionized water, therefore, its whole production cost is the highest, and economic worth is inconspicuous.
[summary of the invention]
The goal of the invention of the present invention is: for the problem of above-mentioned existence, it is provided that a kind of high-insulativity chlorinated polyethylene
Preparation method.The method of the present invention uses follow-on water phase suspension, owing to there is no the neutralization procedure of traditional water phase suspension,
Will not introduce charged ion, thus obtained chlorinated polyethylene product has good insulating properties, specific insulation reaches 1015
More than Ω cm.
To achieve these goals, the technical solution used in the present invention is as follows:
A kind of preparation method of high insulating property chlorinated polyethylene, including chlorination reaction, washing filtering, leach, be centrifuged, dry
Dry step；
Described chlorination reaction is addition water, high density polyethylene (HDPE), dispersant, emulsifying agent, initiator in reactor；Heat up
After 70 DEG C, start to be passed through chlorine carry out chlorination reaction, reaction temperature 90-135 DEG C, 3-4 hour response time；
Described washing filtering be by chlorination reaction after material be cooled to less than 95 DEG C and be transferred to washing kettle, wash 1-with water
After 2 times, filtrate gets washing material；
Described leaching is to be soaked in water in acid-resistant container by washing material, soaks more than 3 hours；
Described being centrifuged is the moisture in the material after using acid proof centrifugal separator to slough immersion；
The described acid proof boiling-bed drying of dry employing.
Preferably, the water used by the water used by described chlorination reaction, the water used by washing filtering, immersion is deionization
Water.
Further, also having the most centrifugal step after described washing filtering, before leaching, described being just centrifuged is to use
The moisture in the material after immersion sloughed by acid proof centrifugal separator；Described leaching is that the material after being just centrifuged is soaked in water
In acid-resistant container, soak more than 3 hours.Increase centrifugal step in process, hydrogen chloride can be made to the greatest extent may be used after centrifugal
Can remove with water, when can make immersion, the leaching effect of hydrochloric acid is more preferable.
The present invention produces chlorinated polyethylene by using water phase suspension to carry out chlorinated polymeric, but enters follow-up deacidification process
Gone technologic improvement, removed floating acid and other impurity of product surface initially with washing filtering, the step for and be not required to
To need washing more than 4-5 time as tradition washing, substantial amounts of water can be saved.Material institute band moisture content can be removed through the most centrifugal after washing
Floating sour with removing further.Certainly do not carry out the most centrifugal can also, but the effect of deacidification can be slightly worse.Then by being soaked in water
Mode, makes the slow acid of chlorinated polyethylene inside particles discharge, and traditional method is to neutralize chlorinated polyethylene grain with alkali
Acid within Zi, and need heating, the time used is more than 4 hours, the most also generates sodium chloride salt, to product
Insulating properties the most unfavorable, after the making of cable, cable uses a period of time easily to bubble；And the present invention uses immersion
Mode, changes into making it discharge by osmosis by the method to inside fire attack dechlorinationization hydrogen, does not introduce electrolyte, for well
Electrical insulating property lay the first stone.Due in production process of the present invention, chlorinated polyethylene material with a certain amount of acid, so just from
The heart, secondary centrifuging and dry device therefor all use acid proof equipment, as long as centrifuge contacts in centrifuge with material
Surfacing be transformed into acid resistant material, the screen cloth being internally provided with is corrosion resistance, can use titanium plate or zirconium plate
Make.Boiling-bed drying can use acid resistance fiberglass drying bed on the market, it would however also be possible to employ the applicant is homemade resistance to
The anlistatig drying bed of acid, and acidproof effect is more preferable, service life is longer.The baking temperature of boiling-bed drying is typically at 110 DEG C
Above, and hydrochloric acid is volatile material, can be divided in dry run, it is ensured that the quality of final products.Therefore, above-mentioned
Technical scheme, by technologic improvement, does not introduce the ionic impurity of electric conductivity, it is ensured that the insulating properties of product, and passes through equipment
Performance propose improve so that it is meet the Production requirement of band acid chlorinated polyethylene.It addition, use above-mentioned production technology, water consumption
Less, producing a still (by 12 tons of calculation of capacity) chlorinated polyethylene can be with using water wisely more than 15 tons than traditional handicraft, moreover it is possible to joint
Save the production time of 5-6 hour.
Further, chlorination reaction is to add 900 weight parts waters, 110-120 weight portion high-density polyethylene in reactor
Alkene, 2.6-3.2 parts per weight dispersing agent, 0.14-0.25 parts by weight Emulsifier, 0.14-0.25 weight portion initiator；It is warming up to 70 DEG C
After start to be passed through chlorine and carry out chlorination reaction, the total amount being passed through chlorine is 120-144 weight portion, reaction temperature 90-135 DEG C, instead
Between Ying Shi 3-4 hour.Described emulsifying agent is the one or several in polyoxyethylene ether, detergent alkylate naphthenic acid sodium and sodium stearate
Kind；Dispersant is polyvinylpyrrolidone and methyl methacrylate.Described initiator be mass ratio be the hydrogen peroxide of 1:4-8
Diisopropylbenzene (DIPB) and dibenzoyl peroxide.
Further, described soak time controlled at 3-6 hour.The time soaked is according to the situation of chlorinated polyethylene particle
Determining, major part material is after soaking 3 hours, and internal hydrochloric acid discharges substantially.But the chlorination for the special trade mark gathers
Ethylene, particle is softer, and internal void is more, it is necessary to extend the time soaked.
Owing to producing the requirement having corrosion resistance and antistatic behaviour to boiling-bed drying, the boiling that present invention preferably uses is done
Dry bed is made up of fiberglass, and it includes anticorrosion internal layer, middle enhancing structure sheaf and appearance aging resistance outer layer；Described anticorrosion internal layer by
Gelatin jet on mould after solidify to form；Strengthening structure sheaf in the middle of described is alternately to be covered bonding by glue and glass fabric
It is composited；Described appearance aging resistance outer layer is to be 100:2-3 mix after to be injected in age resister according to mass ratio by glue
It solidify to form behind middle enhancing structure sheaf surface；
Wherein said glue includes the raw material of following weight portion: vinylite 60-80 part, furfuryl alcohol resin 15-20 part, poly-
Isobutene. 6-10 part, sepiolite fibre 30-45 part, polyethylene glycol methacrylate-styrene polymer copolymer 2-3 part, MDA
3-5 part, 1,4-butanediol diglycidyl ether 15-25 part, boron modified phenolic resin adhesive 6-8 part, graphite powder 0.5-0.8
Part；Described boron modified phenolic resin adhesive is to be made by the raw material of following weight portion: phenol 90-110 part, first
Aldehyde 20-30 part, Firebrake ZB 5-8 part, barium hydroxide 3-5 part, aniline 2-3 part, A151 silane coupler 2-3 part, tackifying resin 4-6
Part.
Further, the manufacture method of described boron modified phenolic resin adhesive is: get out phenol 90-by weight
110 parts, formaldehyde 20-30 part, Firebrake ZB 5-8 part, barium hydroxide 3-5 part, aniline 2-3 part, A151 silane coupler 2-3 part, increasing
Viscosity resin 4-6 part；Phenol 90-110 part, formaldehyde 5-8 part and Firebrake ZB 5-8 part are joined in reactor, while stirring instead
Answer still to add barium hydroxide 3-5 part and aniline 2-3 part makees composite catalyst, stir 15-20 minute；Then reactor is warming up to
75-80 DEG C of reaction 50-60min；It is warming up to 85 DEG C again, adds the formaldehyde of remainder, react 20-30 minute；Then stop adding
Heat, is neutral with the pH value in oxalic acid regulation reactor, in question response still at a temperature of when being down to less than 40 DEG C, addition A151 silicon
Alkane coupling agent 2-3 part, tackifying resin 4-6 part stirring 20-30min, be then filtered off material, i.e. obtain boron modified phenolic resin gluing
Agent.
Further, described age resister is phthalic acid with benzotriazole according to weight ratio is 1-2:1 composition.
The above-mentioned material improvement to drying bed is chosen by glue raw material and is coordinated, and regulates glue medium vinyl tree
Fat, Furanol resin, polyisobutylene, sepiolite fibre, antistatic additive, firming agent, diluent resin, boron modified phenolic resin glue
Part by weight between stick, graphite powder, can make the overall corrosion resistance of drying bed, antistatic effect, resistance to elevated temperatures, strong
Degree and toughness are satisfied by Production requirement.And its boron modification resin used is obtained by phenolic resin modified, there is viscosity
High, strong, the corrosion-resistant and resistant to elevated temperatures performance of caking property, its add together with polyisobutylene can have between each raw material good
Amalgamation, promotes homogeneity and the overall performance of fiberglass.
In sum, owing to have employed technique scheme, the invention has the beneficial effects as follows:
1, the method for the present invention uses follow-on water phase suspension, and follow-up deacidification process has been carried out technologic changing
Enter, owing to there is no the neutralization procedure of traditional water phase suspension, conductive ion and salt will not be introduced, thus obtained chlorination gathers
Ethylene product has good insulating properties, and specific insulation reaches 1015More than Ω cm.
2, the present invention is by proposing to improve to the performance of equipment so that it is meet the production need of band acid chlorinated polyethylene material
Ask.The method using the present invention, owing to concentration of hydrochloric acid is low, so equipment acid resistance is required lower than sour phase suspension method, and product
Finally need not grind.It addition, the method using the present invention, relative to water phase suspension, production technology water consumption is less, produces
One still (by 12 tons of calculation of capacity) chlorinated polyethylene can be with using water wisely more than 15 tons than traditional handicraft, moreover it is possible to save 5-6 hour
Production time.
[detailed description of the invention]
The present invention provides the preparation method of a kind of high insulating property chlorinated polyethylene, including chlorination reaction, washing filtering, leaching
The step going out, being centrifuged, be dried；Described chlorination reaction be in reactor add water, high density polyethylene (HDPE), dispersant, emulsifying agent,
Initiator；Start to be passed through chlorine after being warming up to 70 DEG C and carry out chlorination reaction, reaction temperature 90-135 DEG C, 3-4 hour response time；
Described washing filtering be by chlorination reaction after material be cooled to less than 95 DEG C and be transferred to washing kettle, filter after washing 1-2 time with water
Washing material is got in water outlet；Described leaching is to be soaked in water in acid-resistant container by washing material, soaks more than 3 hours；Described
Centrifugal is the moisture in the material after using acid proof centrifugal separator to slough immersion；The described acid proof boiling of dry employing
Drying bed.The method of the present invention uses follow-on water phase suspension, and follow-up deacidification process has been carried out technologic improvement,
Owing to not having the neutralization procedure of traditional water phase suspension, conductive ion and salt will not be introduced, thus obtained chlorinated polyethylene
Alkene product has good insulating properties, and specific insulation reaches 1015More than Ω cm.
As some embodiments of the present invention, the water used by described chlorination reaction, the water used by washing filtering, soak used
Water be deionized water.
As some embodiments of the present invention, chlorination reaction is to add 900 weight parts waters, 110-120 weight in reactor
Amount part high density polyethylene (HDPE), 2.6-3.2 parts per weight dispersing agent, 0.14-0.25 parts by weight Emulsifier, 0.14-0.25 weight portion draw
Send out agent；Starting to be passed through chlorine after being warming up to 70 DEG C and carry out chlorination reaction, the total amount being passed through chlorine is 120-144 weight portion, reaction
Temperature 90-135 DEG C, 3-4 hour response time.
As some embodiments of the present invention, described emulsifying agent is polyoxyethylene ether, detergent alkylate naphthenic acid sodium and tristearin
One or more in acid sodium；Dispersant is polyvinylpyrrolidone and methyl methacrylate.Described initiator is mass ratio
Di-isopropylbenzene hydroperoxide and dibenzoyl peroxide for 1:4-8.
As some embodiments of the present invention, described soak time controlled at 3-6 hour.
Propose some as some embodiments of the present invention, the also material to boiling-bed drying to improve.
Below by way of detailed description of the invention, the invention will be further described.
Embodiment 1
The preparation method of a kind of high insulating property chlorinated polyethylene, including chlorination reaction, washing filtering, once centrifugal, leaching
Go out, secondary centrifuging, dry step；
Chlorination reaction be in reactor, add 900 weight parts waters, 110 weight portion high density polyethylene (HDPE)s, 2.6 weight portions divide
Powder, 0.14 parts by weight Emulsifier, 0.14 weight portion initiator；Start to be passed through chlorine after being warming up to 70 DEG C and carry out chlorination reaction,
The total amount being passed through chlorine is 120 weight portions, reaction temperature 120 DEG C, 4 hours response time.Described emulsifying agent is 0.06 weight portion
Polyoxyethylene ether and 0.08 weight portion sodium stearate；Dispersant is 2.0 weight account polyethylene ketopyrrolidines and 0.6 weight portion methyl
Acrylic acid methyl ester., described initiator be mass ratio be di-isopropylbenzene hydroperoxide and the dibenzoyl peroxide of 1:4.
Described washing filtering be by chlorination reaction after material be cooled to less than 95 DEG C after be transferred to washing kettle, wash with water
After 2 times, filtrate gets washing material；
Described being once centrifuged is that the washing material acid proof centrifugal separator of employing is sloughed moisture；As long as centrifuge will be from
The surfacing contacted with material in scheming is transformed into acid resistant material, and the screen cloth being internally provided with is corrosion resistance,
Zirconium plate can be used to make.
Described leaching is that the material after being once centrifuged is soaked in water in acid-resistant container, soaks 3 hours.
Described secondary centrifuging is the moisture in the material after using acid proof centrifugal separator to slough immersion；Centrifuge is only
The surfacing contacted with material in centrifuge will be transformed into acid resistant material, the screen cloth being internally provided with is corrosion-resistant
Property, titanium plate or zirconium plate can be used to make.
The described acid proof boiling-bed drying of dry employing, can use the acid proof fiberglass of commercial type to seethe with excitement
Drying bed.
Embodiment 2
The preparation method of a kind of high insulating property chlorinated polyethylene, including chlorination reaction, washing filtering, once centrifugal, leaching
Go out, secondary centrifuging, dry step；
Chlorination reaction be in reactor, add 900 weight parts waters, 120 weight portion high density polyethylene (HDPE)s, 3.2 weight portions divide
Powder, 0.25 parts by weight Emulsifier, 0.25 weight portion initiator；Start to be passed through chlorine after being warming up to 70 DEG C and carry out chlorination reaction,
The total amount being passed through chlorine is 144 weight portions, reaction temperature 135 DEG C, 3 hours response time.Described emulsifying agent is 0.13 weight portion
Polyoxyethylene ether and 0.12 weight portion detergent alkylate naphthenic acid sodium；Dispersant is 2.0 weight account polyethylene ketopyrrolidines and 1.2 weights
Amount part methyl methacrylate, described initiator be mass ratio be di-isopropylbenzene hydroperoxide and the dibenzoyl peroxide of 1:8.
Described washing filtering be by chlorination reaction after material be cooled to less than 95 DEG C after be transferred to washing kettle, wash with water
After 2 times, filtrate gets washing material；
Described being once centrifuged is that the washing material acid proof centrifugal separator of employing is sloughed moisture；As long as centrifuge will be from
The surfacing contacted with material in scheming is transformed into acid resistant material, and the screen cloth being internally provided with is corrosion resistance,
Titanium plate can be used to make.
Described leaching is that the material after being once centrifuged is soaked in water in acid-resistant container, soaks 4 hours；
Described secondary centrifuging is the moisture in the material after using acid proof centrifugal separator to slough immersion；Centrifuge is only
The surfacing contacted with material in centrifuge will be transformed into acid resistant material, the screen cloth being internally provided with is corrosion-resistant
Property, titanium plate can be used to make.
The described acid proof boiling-bed drying of dry employing, can apply the acid resistance antistatic prepared by the following method
Fiberglass boiling-bed drying.Concrete manufacture method is:
(1) preparation boron modified phenolic resin adhesive
Boron modified phenolic resin adhesive is to be made by the raw material of following weight portion: get out benzene by weight
90 parts of phenol, 20 parts of formaldehyde, Firebrake ZB 5 parts, barium hydroxide 3 parts, aniline 2 parts, A151 silane coupler 2 parts, tackifying resin EVA 4
Part；Phenol 90 parts, 5 parts of formaldehyde and Firebrake ZB 5 parts are joined in reactor, adds barium hydroxide 3 at reactor while stirring
Part and aniline 2 parts make composite catalyst, stir 15 minutes；Then reactor is warming up to 75 DEG C of reaction 50min；It is warming up to 85 again
DEG C, add the formaldehyde of remainder, react 20 minutes；Then stop heating, be neutral with the pH value in oxalic acid regulation reactor,
When being down to less than 40 DEG C at a temperature of in question response still, add A151 silane coupler 2 parts, tackifying resin SBS 4 parts stirring
20min, is then filtered off material, i.e. obtains boron modified phenolic resin adhesive.Dissociating of gained boron modified phenolic resin adhesive
Phenol is less than 8%, and free formaldehyde is less than 1.2%.
(2) by weight ratio prepare glue raw material: vinylite 60 parts, furfuryl alcohol resin 15 parts, polyisobutylene 6 parts,
Sepiolite fibre 30 parts, antistatic additive polyethylene glycol methacrylate-styrene polymer copolymer 2 parts, MDA 3 parts, resin are dilute
Releasing agent diluent resin is expoxy propane o-cresyl ether 15 parts, boron modified phenolic resin adhesive 6 parts, graphite powder 0.5 part；With
High speed dispersor stirs 5min with the linear velocity of 15m/s, obtains glue.Glue is divided by the demand in internal layer, intermediate layer and outer layer
Become 3 parts, respectively internal layer glue, intermediate layer glue and outer layer glue, according to glue and ageing-resistant matter in outer layers glue
Amount is more standby than for 100:2 mix homogeneously, and wherein, age resister is phthalic acid with benzotriazole according to weight ratio is 1:1 composition.
(3) using the mode of injection to make drying bed anticorrosion internal layer, the thickness of internal layer is 0.5mm-2mm, this enforcement
Example is 1mm；Then intermediate layer glue is put in maceration tank, after hose lining liquid-solidization, use and be wound around unit, use glass fibre
Cloth impregnates glue while the mode of Stagger-wrap is fabricated to middle enhancing structure sheaf；Structure sheaf surface is finally strengthened in centre
Spraying one layer of glue and ageing-resistant mixture, form appearance aging resistance outer layer after cured, the thickness of outer layer is 0.5mm-
2mm, the present embodiment is 1mm.
Embodiment 3
A kind of preparation method of high insulating property chlorinated polyethylene, including chlorination reaction, washing filtering, leach, be centrifuged, dry
Dry step；
Chlorination reaction be in reactor, add 900 weight parts waters, 115 weight portion high density polyethylene (HDPE)s, 3.0 weight portions divide
Powder, 0.2 parts by weight Emulsifier, 0.2 weight portion initiator；Start to be passed through chlorine after being warming up to 70 DEG C and carry out chlorination reaction, logical
The total amount entering chlorine is 120-144 weight portion, reaction temperature 90 DEG C, 4 hours response time.Described emulsifying agent is 0.13 weight portion
Polyoxyethylene ether and 0.07 weight portion detergent alkylate naphthenic acid sodium；Dispersant is 2.0 weight account polyethylene ketopyrrolidines and 1.0 weights
Amount part methyl methacrylate, described initiator be mass ratio be di-isopropylbenzene hydroperoxide and the dibenzoyl peroxide of 1:6.
Described washing filtering be by chlorination reaction after material be cooled to less than 95 DEG C after be transferred to washing kettle, wash with water
After 2 times, filtrate gets washing material；
Described leaching is to be soaked in water in acid-resistant container by washing material, soaks more than 5 hours；To mixture during immersion
Material is stirred, and hydrochloric acid can be made to accelerate to discharge.
Described being centrifuged is the moisture in the material after using acid proof centrifugal separator to slough immersion；As long as centrifuge will
The surfacing contacted with material in centrifuge is transformed into acid resistant material, and the screen cloth being internally provided with is corrosion resistance
, titanium plate or zirconium plate can be used to make.
The described acid proof boiling-bed drying of dry employing, can apply the acid resistance antistatic prepared by the following method
Fiberglass boiling-bed drying.Concrete manufacture method is:
(1) preparation boron modified phenolic resin adhesive
Boron modified phenolic resin adhesive is to be made by the raw material of following weight portion: get out benzene by weight
110 parts of phenol, 30 parts of formaldehyde, Firebrake ZB 8 parts, barium hydroxide 5 parts, aniline 3 parts, A151 silane coupler 3 parts, tackifying resin EVA
6 parts；Phenol 110 parts, 8 parts of formaldehyde and Firebrake ZB 8 parts are joined in reactor, adds barium hydroxide at reactor while stirring
Make composite catalyst with aniline 3 parts, stir 20 minutes for 5 parts；Then reactor is warming up to 80 DEG C of reaction 50min；It is warming up to again
85 DEG C, add the formaldehyde of remainder, react 30 minutes；Then heating is stopped, in the pH value in oxalic acid regulation reactor being
Property, in question response still at a temperature of when being down to less than 40 DEG C, addition A151 silane coupler 3 parts, tackifying resin 6 parts stirring
30min, is then filtered off material, i.e. obtains boron modified phenolic resin adhesive.Dissociating of gained boron modified phenolic resin adhesive
Phenol is less than 8%, and free formaldehyde is less than 1.2%.
(2) by weight ratio prepare glue raw material: vinylite 80 parts, furfuryl alcohol resin 20 parts, polyisobutylene 10 parts,
Sepiolite fibre 45 parts, antistatic additive polyethylene glycol methacrylate-styrene polymer copolymer 3 parts, MDA 5 parts, resin are dilute
Releasing agent diluent resin is polypropylene glycol diglycidyl ether 25 parts, boron modified phenolic resin adhesive 8 parts, graphite powder 0.8 part；
Stir 10min with high speed dispersor with the linear velocity of 22m/s, obtain glue.Glue is pressed the demand of internal layer, intermediate layer and outer layer
It is divided into 3 parts, respectively internal layer glue, intermediate layer glue and outer layer glue, according to glue with ageing-resistant in outer layers glue
Mass ratio is that 100:3 mix homogeneously is standby, and wherein, age resister is phthalic acid and benzotriazole is 2:1 group according to weight ratio
Become.
(3) using the mode of injection to make drying bed anticorrosion internal layer, the thickness of internal layer is 0.5mm-2mm；Then will
Intermediate layer glue is put in maceration tank, after hose lining liquid-solidization, use and is wound around unit, impregnates glue with glass fabric
The mode of Stagger-wrap is fabricated to middle enhancing structure sheaf on one side；Finally strengthen in centre structure sheaf surface spray one layer of glue with
Ageing-resistant mixture, forms appearance aging resistance outer layer after cured.
In embodiment 2-3, the indices of obtained fiberglass drying bed is the most different, and volumetric resistivity value is about 108
Ω cm, meets anlistatig demand.Corrosion resistance test is carried out over 20 days with the soak with hydrochloric acid of 25% high concentration, considerably beyond dry
Concentration of hydrochloric acid in dry material, result of the test is that fiberglass does not has significant change, it was demonstrated that it has good acid-resistant corrosion.Separately
Its intensity outer and toughness all meet the demand of actual production.
Chlorinated polyethylene obtained in embodiment 1-3, uses HG/T2704-2010 chlorinated polyethylene industry standard to record
Method carry out the detection of properties, table 1 specific as follows:
The performance indications of table 1 chlorinated polyethylene
As can be seen from Table 1, the property indices of the chlorinated polyethylene obtained by embodiment 1-3 all meets country's mark
Standard, and the specific insulation of product is 1015More than Ω cm, has higher insulating properties.
Claims (10)
1. the preparation method of a high insulating property chlorinated polyethylene, it is characterised in that: include chlorination reaction, washing filtering, leaching
The step going out, being centrifuged, be dried；
Described chlorination reaction is addition water, high density polyethylene (HDPE), dispersant, emulsifying agent, initiator in reactor；It is warming up to 70
Start to be passed through chlorine after DEG C and carry out chlorination reaction, reaction temperature 90-135 DEG C, 3-4 hour response time；
Described washing filtering be by chlorination reaction after material be cooled to less than 95 DEG C and be transferred to washing kettle, wash with water 1-2 time
Rear filtrate gets washing material；
Described leaching is to be soaked in water in acid-resistant container by described washing material, soaks more than 3 hours；
Described being centrifuged is the moisture in the material after using acid proof centrifugal separator to slough immersion；
The described acid proof boiling-bed drying of dry employing.
The preparation method of a kind of high insulating property chlorinated polyethylene the most according to claim 1, it is characterised in that: described
Also having the most centrifugal step after washing filtering, before leaching, described being just centrifuged is to use acid proof centrifugal separator to slough
The moisture in material after immersion；Described leaching is that the material after being just centrifuged is soaked in water in acid-resistant container, soaks 3 hours
Above.
The preparation method of a kind of high insulating property chlorinated polyethylene the most according to claim 1 and 2, it is characterised in that: institute
Stating chlorination reaction is to add 900 weight parts waters, 110-120 weight portion high density polyethylene (HDPE), 2.6-3.2 weight portion in reactor
Dispersant, 0.14-0.25 parts by weight Emulsifier, 0.14-0.25 weight portion initiator；Start to be passed through chlorine after being warming up to 70 DEG C to enter
Row chlorination reaction, the total amount being passed through chlorine is 120-144 weight portion, reaction temperature 90-135 DEG C, 3-4 hour response time.
The preparation method of a kind of high insulating property chlorinated polyethylene the most according to claim 1 and 2, it is characterised in that: institute
Being provided with the screen cloth of corrosion resistance in stating the most centrifugal and centrifugal acid proof centrifugal separator used, this screen cloth uses titanium plate or zirconium
Plate is made, and the water used by the water used by described chlorination reaction, the water used by washing filtering, immersion is deionized water.
The preparation method of a kind of high insulating property chlorinated polyethylene the most according to claim 1 and 2, it is characterised in that: institute
State soak time to control at 3-6 hour.
The preparation method of a kind of high insulating property chlorinated polyethylene the most according to claim 1 and 2, it is characterised in that: institute
Stating emulsifying agent is one or more in polyoxyethylene ether, detergent alkylate naphthenic acid sodium and sodium stearate；Dispersant is polyethylene
Ketopyrrolidine and methyl methacrylate.
The preparation method of a kind of high insulating property chlorinated polyethylene the most according to claim 1 and 2, it is characterised in that: institute
State initiator be mass ratio be di-isopropylbenzene hydroperoxide and the dibenzoyl peroxide of 1:4-8.
The preparation method of a kind of high insulating property chlorinated polyethylene the most according to claim 1 and 2, it is characterised in that: institute
State boiling-bed drying and include anticorrosion internal layer, middle enhancing structure sheaf and appearance aging resistance outer layer；Described anticorrosion internal layer is sprayed by glue
It solidify to form after penetrating on mould；Strengthen in the middle of described structure sheaf be alternately covered by glue and glass fabric bonding compound and
Become；Described appearance aging resistance outer layer is to be to be injected in middle increasing after 100:2-3 mixes by glue and age resister according to mass ratio
It solidify to form behind strong structure sheaf surface；
Wherein said glue includes the raw material of following weight portion: vinylite 60-80 part, furfuryl alcohol resin 15-20 part, poly-isobutyl
Alkene 6-10 part, sepiolite fibre 30-45 part, polyethylene glycol methacrylate-styrene polymer copolymer 2-3 part, MDA 3-5
Part, 1,4-butanediol diglycidyl ether 15-25 part, boron modified phenolic resin adhesive 6-8 part, graphite powder 0.5-0.8 part；Institute
The boron modified phenolic resin adhesive stated is to be made by the raw material of following weight portion: phenol 90-110 part, formaldehyde 20-
30 parts, Firebrake ZB 5-8 part, barium hydroxide 3-5 part, aniline 2-3 part, A151 silane coupler 2-3 part, tackifying resin 4-6 part.
The preparation method of a kind of high insulating property chlorinated polyethylene the most according to claim 7, it is characterised in that: described boron
The manufacture method of modified phenolic resin adhesive is: get out phenol 90-110 part, formaldehyde 20-30 part, Firebrake ZB by weight
5-8 part, barium hydroxide 3-5 part, aniline 2-3 part, A151 silane coupler 2-3 part, tackifying resin 4-6 part；By phenol 90-110
Part, formaldehyde 5-8 part and Firebrake ZB 5-8 part join in reactor, add barium hydroxide 3-5 part and benzene at reactor while stirring
Amine 2-3 part makees composite catalyst, stirs 15-20 minute；Then reactor is warming up to 75-80 DEG C of reaction 50-60min；Rise again
Temperature, to 85 DEG C, adds the formaldehyde of remainder, reacts 20-30 minute；Then heating is stopped, with the pH in oxalic acid regulation reactor
Value is neutrality, in question response still at a temperature of when being down to less than 40 DEG C, addition A151 silane coupler 2-3 part, tackifying resin 4-6
Part stirring 20-30min, is then filtered off material, i.e. obtains boron modified phenolic resin adhesive.
The preparation method of a kind of high insulating property chlorinated polyethylene the most according to claim 7, it is characterised in that: described
Age resister is phthalic acid with benzotriazole according to weight ratio is 1-2:1 composition.
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| CN112079945A (en) * | 2020-09-09 | 2020-12-15 | 安徽华纳化学工业有限公司 | Chlorinated polyethylene manufacturing process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101831019A (en) * | 2010-05-13 | 2010-09-15 | 潍坊亚星集团有限公司 | Preparation method of rubber type chlorinated polyethylene with high electrical property |
| CN101899124A (en) * | 2010-07-12 | 2010-12-01 | 杭州科利化工有限公司 | Preparation method of chlorinated polyethylene rubber with high insulation |
| CN102786610A (en) * | 2012-07-10 | 2012-11-21 | 苏州宝津塑业有限公司 | Method for synthesizing CPVC resin by gas-solid phase method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831019A (en) * | 2010-05-13 | 2010-09-15 | 潍坊亚星集团有限公司 | Preparation method of rubber type chlorinated polyethylene with high electrical property |
| CN101899124A (en) * | 2010-07-12 | 2010-12-01 | 杭州科利化工有限公司 | Preparation method of chlorinated polyethylene rubber with high insulation |
| CN102786610A (en) * | 2012-07-10 | 2012-11-21 | 苏州宝津塑业有限公司 | Method for synthesizing CPVC resin by gas-solid phase method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112079945A (en) * | 2020-09-09 | 2020-12-15 | 安徽华纳化学工业有限公司 | Chlorinated polyethylene manufacturing process |
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