CN105837713B - A kind of preparation method of high-insulativity haloflex - Google Patents
A kind of preparation method of high-insulativity haloflex Download PDFInfo
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- CN105837713B CN105837713B CN201610372772.7A CN201610372772A CN105837713B CN 105837713 B CN105837713 B CN 105837713B CN 201610372772 A CN201610372772 A CN 201610372772A CN 105837713 B CN105837713 B CN 105837713B
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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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- 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
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Abstract
The present invention provides a kind of preparation method of high-insulativity haloflex, belongs to the production technical field of haloflex.This method include chlorination reaction, washing filtering, leaching, centrifugation, drying step；The washing filtering is transferred in washing kettle after the material after chlorination reaction is cooled to 95 DEG C or less, and material must be washed by filtering out moisture after being washed with water once；The leaching is will to wash material to be soaked in water in acid-resistant container, impregnate 3 hours or more；The centrifugation is the moisture sloughed using acid proof centrifugal separator in the material after impregnating；It is described dry using acid proof boiling-bed drying.The obtained haloflex product of the present invention has a good insulating properties, and volume resistivity is up to 1015Ω cm or more.
Description
【Technical field】
The present invention relates to the production technical fields of haloflex, and in particular to a kind of system of high-insulativity haloflex
Preparation Method.
【Background technology】
Electric wire is general power transmission material, is required to the insulation performance for having certain in use.Electric wire electricity
The common insulating materials of cable has thermoplastic elastomer (TPE) (TPE), polyvinyl chloride (PVC), low density polyethylene (LDPE) (LDPE), crosslinking synthesis
Polymer (XL), haloflex (CPE) and ethylene propylene diene rubber etc..Wherein, haloflex (CPE) is by high-density polyethylene
Alkene (HDPE) is through high molecular material made from chlorination substitution reaction.
CPE has excellent weatherability, resistance to ozone, chemical-resistant resistance and ageing-resistant performance, and oil resistivity, flame retardant property are good,
With other high molecular materials such as PVC, PE and SR can mixing in varing proportions, high comprehensive performance.It is used in haloflex
In in terms of electric wire, in the early time in order to ensure the insulation performance of electric wire, mostly made using ethylene propylene diene rubber, due to EPDM
Glue price is very high, develop to later it is mixed by a certain percentage with EPDM using chlorinated polyethylene rubber, how in formula
More using the chlorinated polyethylene rubber of low price or completely using chlorinated polyethylene rubber to reduce overall cost just in system
It is a critically important subject under discussion, the ratio of chlorinated polyethylene rubber in formula is determined by its electrical insulation capability, electrical insulation capability
More caing be compared to example can bigger or even complete substitution.
The insulating properties of haloflex has certain relationship with its production technology.Haloflex (CPE) produces work at present
Skill mainly has water phase suspension and sour phase suspension method, traditional water phase suspension to pass through the processes such as depickling, neutralization, dealkalize, meeting
More conductive ion is brought, and these conductive ions can not completely remove, has larger impact to electric property.Using acid phase process
Production can reduce the content of charged ion, and the Chinese patent of Publication No. CN101831019A discloses a kind of " high electricality
The preparation method of energy rubber-type chlorinated polyethylene ", this method produces haloflex using sour phase suspension method, passes through
Deionized water is used in cleaning product, improves the insulation performance of product to a certain extent, however although acid phase process does not have
The process of neutralization does not generate charged ion, but it without cleaning, the process impregnated, deacidification is not thorough, has to the performance of product
The problem of harmful effect, product storage is susceptible to product jaundice in 3-6 months.
In addition, using sour phase suspension method since concentration of the product containing acid is higher (about 28%), follow-up vacuum filter used
The equipment such as machine, centrifuge, drying machine are required to be made of the extraordinary material of acid resistance, and investment cost is very high, and the party
Material particle made from method is thicker, needs to be ground it, needs to expend more electric energy, its production in addition will use special
Deionized water, therefore, entire production cost are also very high, economic value unobvious.
【Invention content】
The goal of the invention of the present invention is：In view of the above problems, a kind of high-insulativity haloflex is provided
Preparation method.The method of the present invention uses follow-on water phase suspension, due to there is no the neutralization procedure of traditional water phase suspension method,
Charged ion will not be introduced, thus obtained haloflex product has a good insulating properties, volume resistivity is up to 1015
Ω cm or more.
To achieve the goals above, the technical solution adopted by the present invention is as follows：
A kind of preparation method of high insulating property haloflex, including it is chlorination reaction, washing filtering, leaching, centrifugation, dry
Dry step；
The chlorination reaction is that water, high density polyethylene (HDPE), dispersant, emulsifier, initiator are added into reaction kettle；Heating
Start to be passed through chlorine progress chlorination reaction, 90-135 DEG C of reaction temperature, reaction time 3-4 hour after to 70 DEG C；
The washing filtering is that the material after chlorination reaction is cooled to 95 DEG C or less to be transferred to washing kettle, and 1- is washed with water
Moisture is filtered out after 2 times must wash material；
The leaching is will to wash material to be soaked in water in acid-resistant container, impregnate 3 hours or more；
The centrifugation is the moisture sloughed using acid proof centrifugal separator in the material after impregnating；
It is described dry using acid proof boiling-bed drying.
Preferably, the water used in the chlorination reaction, the water used in washing filtering, the water used in immersion are deionization
Water.
Further, there is first the step of centrifuging after the washing filtering, before leaching, the just centrifugation is to use
Acid proof centrifugal separator sloughs the moisture in the material after impregnating；The leaching is that the material after first centrifugation is soaked in water
In acid-resistant container, impregnate 3 hours or more.The step of increasing centrifugation in process, can by using up hydrogen chloride after centrifugation
It can be removed with water, when can make immersion, the leaching effect of hydrochloric acid is more preferable.
The present invention by using water phase suspension come chlorinated polymeric produce haloflex, but to subsequent deacidification process into
Gone technologic improvement, washing filtering used to remove the floating acid of product surface and other impurity first, the step for and be not required to
Washing 4-5 times or more is needed as tradition washing, a large amount of water can be saved.After washing material institute band moisture content can be removed through just centrifugation
Floating acid is removed with further.Certainly without just centrifuge can also, but deacidify effect can be slightly worse.Then by being soaked in water
Mode makes the slow acid of haloflex inside particles release, and traditional method is to neutralize haloflex grain with alkali
Acid inside son, and need to heat, the time used is 4 hours or more, sodium chloride salt is also generated in the process, to product
Insulating properties it is very unfavorable, for cable making after, cable using a period of time be easy blistering；And the present invention is using immersion
Mode will be changed to make it release by osmosis, do not introduce electrolyte, be good to the method for inside fire attack dechlorinationization hydrogen
Electrical insulating property lay the first stone.Due in production process of the present invention, haloflex material carries a certain amount of acid, thus just from
The heart, secondary centrifuging and dry device therefor are all made of acid proof equipment, as long as centrifuge will contact in centrifuge with material
Surfacing be transformed into acid resistant material, the sieve being internally provided with is corrosion resistance, can be used titanium plate or zirconium plate
It is made.Acid resistance fiberglass drying bed on the market may be used in boiling-bed drying, the applicant can also be used homemade resistance to
The anlistatig drying bed of acid, and acidproof effect is more preferable, the service life is longer.The drying temperature of boiling-bed drying is generally at 110 DEG C
More than, and hydrochloric acid is volatile substance, can be divided in the drying process, ensures the quality of final products.Therefore, above-mentioned
Technical solution does not introduce the ionic impurity of electric conductivity by technologic improvement, ensures the insulation performance of product, and passes through equipment
Performance propose improve, make its meet band acid haloflex production requirement.In addition, using above-mentioned production technology, water consumption
Less, producing a kettle (press 12 tons of calculation of capacity) haloflex can be with 15 tons of using water wisely or more than traditional handicraft, moreover it is possible to save
Save 5-6 hours production times.
Further, chlorination reaction is that 900 parts by weight water, 110-120 parts by weight high-density polyethylenes are added into reaction kettle
Alkene, 2.6-3.2 parts per weight dispersing agents, 0.14-0.25 parts by weight Emulsifier, 0.14-0.25 parts by weight initiators；It is warming up to 70 DEG C
After start to be passed through chlorine and carry out chlorination reaction, the total amount for being passed through chlorine is 120-144 parts by weight, 90-135 DEG C of reaction temperature, instead
3-4 hours between seasonable.The emulsifier is polyoxyethylene ether, detergent alkylate naphthenic acid sodium and one kind or several in odium stearate
Kind；Dispersant is polyvinylpyrrolidone and methyl methacrylate.The initiator is that mass ratio is 1:The hydrogen peroxide of 4-8
Diisopropylbenzene (DIPB) and dibenzoyl peroxide.
Further, the soaking time control was at 3-6 hours.The case where time of immersion is according to haloflex particle
It determines, after impregnating 3 hours, internal hydrochloric acid releases most of material substantially.But it is poly- for the chlorination of the special trade mark
Ethylene, particle is softer, and internal void is more, it is necessary to extend the time of immersion.
Since production has boiling-bed drying the requirement of corrosion resistance and antistatic property, present invention preferably uses boiling it is dry
Dry bed is made of fiberglass comprising anti-corrosion internal layer, intermediate enhancing structure layer and the anti-aging outer layer of appearance；The anti-corrosion internal layer by
Gelatin jet on mold after be formed by curing；The intermediate enhancing structure layer is to replace covering with glass fabric by glue to bond
It is combined；It according to mass ratio is 100 that the anti-aging outer layer of appearance, which is by glue and age resister,:It is injected in after 2-3 mixing
It is formed by curing after intermediate enhancing structure layer surface；
The wherein described glue includes the raw material of following parts by weight：60-80 parts of vinylite, gathers 15-20 parts of furfuryl alcohol resin
6-10 parts of isobutene, 30-45 parts of sepiolite fibre, 2-3 parts of polyethylene glycol methacrylate-styrene polymer copolymer, diaminodiphenylmethane
3-5 parts, 15-25 parts of 1,4- butanediol diglycidyl ethers, 6-8 parts of boron modified phenolic resin adhesive, graphite powder 0.5-0.8
Part；The boron modified phenolic resin adhesive is made by the raw material of following parts by weight：90-110 parts of phenol, first
20-30 parts of aldehyde, 5-8 parts of zinc borate, 3-5 parts of barium hydroxide, 2-3 parts of aniline, 2-3 parts of A151 silane coupling agents, tackifying resin 4-6
Part.
Further, the production method of the boron modified phenolic resin adhesive is：It gets out phenol 90- by weight
110 parts, 20-30 parts of formaldehyde, 5-8 parts of zinc borate, 3-5 parts of barium hydroxide, 2-3 parts of aniline, 2-3 parts of A151 silane coupling agents, increase
4-6 parts of viscosity resin；5-8 parts of 90-110 parts of phenol, 5-8 parts of formaldehyde and zinc borate are added in reaction kettle, while stirring anti-
It answers kettle that 3-5 parts of barium hydroxide is added and makees composite catalyst with 2-3 parts of aniline, stir 15-20 minutes；Then reaction kettle is warming up to
75-80 DEG C of reaction 50-60min；It is warming up to 85 DEG C again, the formaldehyde of remainder is added, reacts 20-30 minutes；Then stop adding
Heat, it is neutral to adjust the pH value in reaction kettle with oxalic acid, and when being down to 40 DEG C or less at the temperature in reaction kettle, A151 silicon is added
2-3 parts of alkane coupling agent, 4-6 parts of tackifying resin stirring 20-30min, then filtering and discharging is to get to boron modified phenolic resin gluing
Agent.
Further, it is 1-2 that the age resister, which is phthalic acid with benzotriazole according to weight ratio,:1 composition.
The above-mentioned material improvement to drying bed adjusts glue medium vinyl tree by the selection and cooperation of glue raw material
Fat, furans polyimide resin, polyisobutene, sepiolite fibre, antistatic agent, curing agent, diluent resin, boron modified phenolic resin glue
Weight ratio between stick, graphite powder can make the corrosion resistance of drying bed entirety, antistatic effect, high temperature resistance, strong
Degree and toughness are satisfied by production requirement.And the boron modification resin used in it is obtained by phenolic resin modified, has viscosity
It is high, caking property is strong, corrosion-resistant and heat safe performance, together with polyisobutene addition can have between each raw material good
Amalgamation promotes the homogeneity and overall performance of fiberglass.
In conclusion by adopting the above-described technical solution, the beneficial effects of the invention are as follows：
1, method of the invention uses follow-on water phase suspension, and technologic change has been carried out to subsequent deacidification process
Into, due to not having the neutralization procedure of traditional water phase suspension method, conductive ion and salt will not be introduced, thus obtained chlorination is poly-
Ethylene product has good insulating properties, and volume resistivity is up to 1015Ω cm or more.
2, the present invention proposes to improve by the performance to equipment, it is made to meet the production need with sour haloflex material
It asks.Method using the present invention, since concentration of hydrochloric acid is low, thus it is lower than sour phase suspension method to the requirement of equipment acid resistance, and product
It need not finally grind.In addition, using the method for the present invention, relative to water phase suspension, production technology water consumption is less, production
One kettle (press 12 tons of calculation of capacity) haloflex can be with 15 tons of using water wisely or more than traditional handicraft, moreover it is possible to save 5-6 hours
Production time.
【Specific implementation mode】
The present invention provides a kind of preparation method of high insulating property haloflex, including chlorination reaction, washing filtering, leaching
The step go out, centrifuge, dried；The chlorination reaction be into reaction kettle be added water, high density polyethylene (HDPE), dispersant, emulsifier,
Initiator；Start to be passed through chlorine progress chlorination reaction, 90-135 DEG C of reaction temperature, reaction time 3-4 hour after being warming up to 70 DEG C；
The washing filtering is that the material after chlorination reaction is cooled to 95 DEG C or less to be transferred to washing kettle, filter after being washed with water 1-2 times
Washing material is got in water outlet；The leaching is will to wash material to be soaked in water in acid-resistant container, impregnate 3 hours or more；It is described
Centrifugation is the moisture sloughed using acid proof centrifugal separator in the material after impregnating；It is described dry using acid proof boiling
Drying bed.The method of the present invention uses follow-on water phase suspension, and technologic improvement has been carried out to subsequent deacidification process,
Due to not having the neutralization procedure of traditional water phase suspension method, conductive ion and salt, thus obtained chlorinated polyethylene will not be introduced
Alkene product has good insulating properties, and volume resistivity is up to 1015Ω cm or more.
As some embodiments of the present invention, the water used in water, washing filtering used in the chlorination reaction, used in immersion
Water be deionized water.
As some embodiments of the present invention, chlorination reaction is that 900 parts by weight water, 110-120 weights are added into reaction kettle
Amount part high density polyethylene (HDPE), 2.6-3.2 parts per weight dispersing agents, 0.14-0.25 parts by weight Emulsifier, 0.14-0.25 parts by weight are drawn
Send out agent；Start to be passed through chlorine progress chlorination reaction after being warming up to 70 DEG C, the total amount for being passed through chlorine is 120-144 parts by weight, reaction
90-135 DEG C of temperature, reaction time 3-4 hour.
As some embodiments of the present invention, the emulsifier is polyoxyethylene ether, detergent alkylate naphthenic acid sodium and tristearin
One or more of sour sodium；Dispersant is polyvinylpyrrolidone and methyl methacrylate.The initiator is mass ratio
It is 1:The di-isopropylbenzene hydroperoxide and dibenzoyl peroxide of 4-8.
As some embodiments of the present invention, the soaking time control was at 3-6 hours.
As some embodiments of the present invention, some improvement also are proposed to the material of boiling-bed drying.
Below by way of specific implementation mode, the invention will be further described.
Embodiment 1
A kind of preparation method of high insulating property haloflex, including chlorination reaction, washing filtering, primary centrifugation, leaching
Go out, secondary centrifuging, the step of drying；
Chlorination reaction is that 900 parts by weight water, 110 parts by weight high density polyethylene (HDPE)s, 2.6 parts by weight point are added into reaction kettle
Powder, 0.14 parts by weight Emulsifier, 0.14 parts by weight initiator；Start to be passed through chlorine progress chlorination reaction after being warming up to 70 DEG C,
The total amount for being passed through chlorine is 120 parts by weight, 120 DEG C of reaction temperature, 4 hours reaction time.The emulsifier is 0.06 parts by weight
Polyoxyethylene ether and 0.08 parts by weight odium stearate；Dispersant is 2.0 weight account polyethylene pyrrolidones and 0.6 parts by weight methyl
Methyl acrylate, the initiator are that mass ratio is 1:4 di-isopropylbenzene hydroperoxide and dibenzoyl peroxide.
The washing filtering is to be transferred to washing kettle after the material after chlorination reaction is cooled to 95 DEG C or less, is washed with water
Moisture is filtered out after 2 times must wash material；
The primary centrifugation is will to wash material to slough moisture using acid proof centrifugal separator；As long as centrifuge will be from
The surfacing contacted with material in scheming is transformed into acid resistant material, and the sieve being internally provided with is corrosion resistance,
Zirconium plate can be used to be made.
The leaching is that the material after primary centrifugation is soaked in water in acid-resistant container, is impregnated 3 hours.
The secondary centrifuging is the moisture sloughed using acid proof centrifugal separator in the material after impregnating；Centrifuge is only
The surfacing contacted with material in centrifuge is transformed into acid resistant material, the sieve being internally provided with is corrosion-resistant
Property, titanium plate can be used or zirconium plate is made.
It is described dry using acid proof boiling-bed drying, the acid proof fiberglass boiling of commercial type may be used
Drying bed.
Embodiment 2
A kind of preparation method of high insulating property haloflex, including chlorination reaction, washing filtering, primary centrifugation, leaching
Go out, secondary centrifuging, the step of drying；
Chlorination reaction is that 900 parts by weight water, 120 parts by weight high density polyethylene (HDPE)s, 3.2 parts by weight point are added into reaction kettle
Powder, 0.25 parts by weight Emulsifier, 0.25 parts by weight initiator；Start to be passed through chlorine progress chlorination reaction after being warming up to 70 DEG C,
The total amount for being passed through chlorine is 144 parts by weight, 135 DEG C of reaction temperature, 3 hours reaction time.The emulsifier is 0.13 parts by weight
Polyoxyethylene ether and 0.12 parts by weight detergent alkylate naphthenic acid sodium；Dispersant is 2.0 weight account polyethylene pyrrolidones and 1.2 weights
Part methyl methacrylate is measured, the initiator is that mass ratio is 1:8 di-isopropylbenzene hydroperoxide and dibenzoyl peroxide.
The washing filtering is to be transferred to washing kettle after the material after chlorination reaction is cooled to 95 DEG C or less, is washed with water
Moisture is filtered out after 2 times must wash material；
The primary centrifugation is will to wash material to slough moisture using acid proof centrifugal separator；As long as centrifuge will be from
The surfacing contacted with material in scheming is transformed into acid resistant material, and the sieve being internally provided with is corrosion resistance,
Titanium plate can be used to be made.
The leaching is that the material after primary centrifugation is soaked in water in acid-resistant container, is impregnated 4 hours；
The secondary centrifuging is the moisture sloughed using acid proof centrifugal separator in the material after impregnating；Centrifuge is only
The surfacing contacted with material in centrifuge is transformed into acid resistant material, the sieve being internally provided with is corrosion-resistant
Property, titanium plate can be used and be made.
It is described dry using acid proof boiling-bed drying, it can be antistatic using acid resistance obtained by the following method
Fiberglass boiling-bed drying.Specifically production method is：
(1) boron modified phenolic resin adhesive is prepared
Boron modified phenolic resin adhesive is made by the raw material of following parts by weight：It gets out benzene by weight
90 parts of phenol, 20 parts of formaldehyde, 5 parts of zinc borate, 3 parts of barium hydroxide, 2 parts of aniline, 2 parts of A151 silane coupling agents, tackifying resin EVA 4
Part；5 parts of 90 parts of phenol, 5 parts of formaldehyde and zinc borate are added in reaction kettle, barium hydroxide 3 is added in reaction kettle while stirring
2 parts of part and aniline make composite catalyst, stir 15 minutes；Then reaction kettle is warming up to 75 DEG C of reaction 50min；It is warming up to 85 again
DEG C, the formaldehyde of remainder is added, reacts 20 minutes；Then stop heating, it is neutrality to adjust the pH value in reaction kettle with oxalic acid,
When being down to 40 DEG C or less at the temperature in reaction kettle, 4 parts of 2 parts of A151 silane coupling agents, tackifying resin SBS stirrings are added
20min, then filtering and discharging is to get to boron modified phenolic resin adhesive.Gained boron modified phenolic resin adhesive dissociates
Phenol is less than 8%, and free formaldehyde is less than 1.2%.
(2) ratio prepares glue raw material by weight：60 parts of vinylite, 15 parts of furfuryl alcohol resin, 6 parts of polyisobutene,
30 parts of sepiolite fibre, 2 parts of antistatic agent polyethylene glycol methacrylate-styrene polymer copolymer, 3 parts of diaminodiphenylmethane, resin are dilute
It is 15 parts of propylene oxide o-cresyl ether, 6 parts of boron modified phenolic resin adhesive, 0.5 part of graphite powder to release agent diluent resin；With
High speed dispersor stirs 5min with the linear velocity of 15m/s, obtains glue.By glue by the demand point of internal layer, middle layer and outer layer
At 3 parts, respectively internal layer glue, middle layer glue and outer layer glue, according to the matter of glue and age resister in outer layers glue
Amount is than being 100:2 be uniformly mixed it is spare, wherein it is 1 that age resister, which is phthalic acid with benzotriazole according to weight ratio,:1 composition.
(3) drying bed anti-corrosion internal layer is made by the way of injection, the thickness of internal layer is 0.5mm-2mm, this implementation
Example is 1mm；Then middle layer glue is put into dipping tank, after the solidification of internal layer glue, using winding unit, uses glass fibre
The mode that cloth is Stagger-wraped on one side impregnate glue while is fabricated to intermediate enhancing structure layer；Finally in intermediate enhancing structure layer surface
The mixture of one layer of glue and age resister is sprayed, forms the anti-aging outer layer of appearance after cured, the thickness of outer layer is 0.5mm-
2mm, the present embodiment 1mm.
Embodiment 3
A kind of preparation method of high insulating property haloflex, including it is chlorination reaction, washing filtering, leaching, centrifugation, dry
Dry step；
Chlorination reaction is that 900 parts by weight water, 115 parts by weight high density polyethylene (HDPE)s, 3.0 parts by weight point are added into reaction kettle
Powder, 0.2 parts by weight Emulsifier, 0.2 parts by weight initiator；Start to be passed through chlorine progress chlorination reaction after being warming up to 70 DEG C, lead to
The total amount for entering chlorine is 120-144 parts by weight, 90 DEG C of reaction temperature, 4 hours reaction time.The emulsifier is 0.13 parts by weight
Polyoxyethylene ether and 0.07 parts by weight detergent alkylate naphthenic acid sodium；Dispersant is 2.0 weight account polyethylene pyrrolidones and 1.0 weights
Part methyl methacrylate is measured, the initiator is that mass ratio is 1:6 di-isopropylbenzene hydroperoxide and dibenzoyl peroxide.
The washing filtering is to be transferred to washing kettle after the material after chlorination reaction is cooled to 95 DEG C or less, is washed with water
Moisture is filtered out after 2 times must wash material；
The leaching is will to wash material to be soaked in water in acid-resistant container, impregnate 5 hours or more；To mixture when immersion
Material is stirred, and hydrochloric acid quickening can be made to release.
The centrifugation is the moisture sloughed using acid proof centrifugal separator in the material after impregnating；As long as centrifuge will
The surfacing contacted with material in centrifuge is transformed into acid resistant material, and the sieve being internally provided with is corrosion resistance
, titanium plate can be used or zirconium plate is made.
It is described dry using acid proof boiling-bed drying, it can be antistatic using acid resistance obtained by the following method
Fiberglass boiling-bed drying.Specifically production method is：
(1) boron modified phenolic resin adhesive is prepared
Boron modified phenolic resin adhesive is made by the raw material of following parts by weight：It gets out benzene by weight
110 parts of phenol, 30 parts of formaldehyde, 8 parts of zinc borate, 5 parts of barium hydroxide, 3 parts of aniline, 3 parts of A151 silane coupling agents, tackifying resin EVA
6 parts；8 parts of 110 parts of phenol, 8 parts of formaldehyde and zinc borate are added in reaction kettle, barium hydroxide is added in reaction kettle while stirring
5 parts are made composite catalyst with 3 parts of aniline, are stirred 20 minutes；Then reaction kettle is warming up to 80 DEG C of reaction 50min；It is warming up to again
85 DEG C, the formaldehyde of remainder is added, reacts 30 minutes；Then stop heating, in being with the pH value in oxalic acid adjusting reaction kettle
Property, when being down to 40 DEG C or less at the temperature in reaction kettle, 6 parts of 3 parts of A151 silane coupling agents, tackifying resin stirrings are added
30min, then filtering and discharging is to get to boron modified phenolic resin adhesive.Gained boron modified phenolic resin adhesive dissociates
Phenol is less than 8%, and free formaldehyde is less than 1.2%.
(2) ratio prepares glue raw material by weight：80 parts of vinylite, 20 parts of furfuryl alcohol resin, 10 parts of polyisobutene,
45 parts of sepiolite fibre, 3 parts of antistatic agent polyethylene glycol methacrylate-styrene polymer copolymer, 5 parts of diaminodiphenylmethane, resin are dilute
It is 25 parts of polypropylene glycol diglycidyl ether, 8 parts of boron modified phenolic resin adhesive, 0.8 part of graphite powder to release agent diluent resin；
10min is stirred with the linear velocity of 22m/s with high speed dispersor, obtains glue.By glue by internal layer, the demand of middle layer and outer layer
It is divided into 3 parts, respectively internal layer glue, middle layer glue and outer layer glue, according to glue and age resister in outer layers glue
Mass ratio is 100:3 be uniformly mixed it is spare, wherein it is 2 that age resister, which is phthalic acid with benzotriazole according to weight ratio,:1 group
At.
(3) drying bed anti-corrosion internal layer is made by the way of injection, the thickness of internal layer is 0.5mm-2mm；Then will
Middle layer glue is put into dipping tank, after the solidification of internal layer glue, using winding unit, impregnates glue on one side with glass fabric
The mode of one side Stagger-wrap is fabricated to intermediate enhancing structure layer；Finally intermediate enhancing structure layer surface spray one layer of glue with
The mixture of age resister forms the anti-aging outer layer of appearance after cured.
In embodiment 2-3, the indices of obtained fiberglass drying bed are more different, and volumetric resistivity value is about 108
Ω cm meet anlistatig demand.Corrosion resistance test is carried out with the salt acid soak of 25% high concentration over 20 days, considerably beyond dry
Concentration of hydrochloric acid in dry material, test result, which is fiberglass, does not have significant change, it was demonstrated that it is with good acid-resistant corrosion.Separately
Its outer intensity and toughness all meet the needs of actual production.
Obtained haloflex in embodiment 1-3, is recorded using HG/T2704-2010 haloflex professional standards
Method carry out the detection of properties, table 1 specific as follows：
The performance indicator of 1 haloflex of table
As can be seen from Table 1, the property indices of the haloflex obtained by embodiment 1-3 meet national mark
Standard, and the volume resistivity of product is 1015Ω cm or more have higher insulating properties.
Claims (9)
1. a kind of preparation method of high insulating property haloflex, it is characterised in that：Including chlorination reaction, washing filtering, leaching
The step go out, centrifuge, dried；
The chlorination reaction is that water, high density polyethylene (HDPE), dispersant, emulsifier, initiator are added into reaction kettle；It is warming up to 70
Start to be passed through chlorine progress chlorination reaction, 90-135 DEG C of reaction temperature, reaction time 3-4 hour after DEG C；
The washing filtering is that the material after chlorination reaction is cooled to 95 DEG C or less to be transferred to washing kettle, is washed with water 1-2 times
After filter out moisture and must wash material；
The leaching is that the washing material is soaked in water in acid-resistant container, impregnate 3 hours or more；
The centrifugation is the moisture sloughed using acid proof centrifugal separator in the material after impregnating；
It is described dry using acid proof boiling-bed drying；
The boiling-bed drying includes anti-corrosion internal layer, intermediate enhancing structure layer and the anti-aging outer layer of appearance；The anti-corrosion internal layer by
Gelatin jet on mold after be formed by curing；The intermediate enhancing structure layer is to replace covering with glass fabric by glue to bond
It is combined；It according to mass ratio is 100 that the anti-aging outer layer of appearance, which is by glue and age resister,:It is injected in after 2-3 mixing
It is formed by curing after intermediate enhancing structure layer surface；
The wherein described glue includes the raw material of following parts by weight：60-80 parts of vinylite, 15-20 parts of furfuryl alcohol resin, poly- isobutyl
6-10 parts of alkene, 30-45 parts of sepiolite fibre, 2-3 parts of polyethylene glycol methacrylate-styrene polymer copolymer, diaminodiphenylmethane 3-5
Part, 15-25 parts of 1,4- butanediol diglycidyl ethers, 6-8 parts of boron modified phenolic resin adhesive, 0.5-0.8 parts of graphite powder；Institute
The boron modified phenolic resin adhesive stated is made by the raw material of following parts by weight：90-110 parts of phenol, formaldehyde 20-
30 parts, 5-8 parts of zinc borate, 3-5 parts of barium hydroxide, 2-3 parts of aniline, 2-3 parts of A151 silane coupling agents, 4-6 parts of tackifying resin.
2. a kind of preparation method of high insulating property haloflex according to claim 1, it is characterised in that：Described
There is the step of just centrifugation after washing filtering, before leaching, the just centrifugation is sloughed using acid proof centrifugal separator
The moisture in material after immersion；The leaching is that the material after first centrifugation is soaked in water in acid-resistant container, is impregnated 3 hours
More than.
3. a kind of preparation method of high insulating property haloflex according to claim 1 or 2, it is characterised in that：Institute
It is that 900 parts by weight water, 110-120 parts by weight high density polyethylene (HDPE), 2.6-3.2 parts by weight are added into reaction kettle to state chlorination reaction
Dispersant, 0.14-0.25 parts by weight Emulsifier, 0.14-0.25 parts by weight initiators；Start to be passed through after being warming up to 70 DEG C chlorine into
Row chlorination reaction, the total amount for being passed through chlorine are 120-144 parts by weight, 90-135 DEG C of reaction temperature, reaction time 3-4 hour.
4. a kind of preparation method of high insulating property haloflex according to claim 1 or 2, it is characterised in that：Institute
The sieve that corrosion resistance is equipped in the acid proof centrifugal separator used in just centrifugation and centrifugation is stated, which uses titanium plate or zirconium
Plate is made, and the water used in water, washing filtering, the water used in immersion used in the chlorination reaction are deionized water.
5. a kind of preparation method of high insulating property haloflex according to claim 1 or 2, it is characterised in that：Institute
Soaking time control is stated at 3-6 hours.
6. a kind of preparation method of high insulating property haloflex according to claim 1 or 2, it is characterised in that：Institute
It is one or more of polyoxyethylene ether and odium stearate to state emulsifier；Dispersant is polyvinylpyrrolidone and metering system
Sour methyl esters.
7. a kind of preparation method of high insulating property haloflex according to claim 1 or 2, it is characterised in that：Institute
It is 1 that state initiator, which be mass ratio,:The di-isopropylbenzene hydroperoxide and dibenzoyl peroxide of 4-8.
8. a kind of preparation method of high insulating property haloflex according to claim 1, it is characterised in that：The boron
The production method of modified phenolic resin adhesive is：It gets out 90-110 parts of phenol, 20-30 parts of formaldehyde, zinc borate by weight
5-8 parts, 3-5 parts of barium hydroxide, 2-3 parts of aniline, 2-3 parts of A151 silane coupling agents, 4-6 parts of tackifying resin；By phenol 90-110
5-8 parts of part, 5-8 parts of formaldehyde and zinc borate are added in reaction kettle, and 3-5 parts of barium hydroxide and benzene is added in reaction kettle while stirring
2-3 parts of amine makees composite catalyst, stirs 15-20 minutes；Then reaction kettle is warming up to 75-80 DEG C of reaction 50-60min；It rises again
The formaldehyde of remainder is added to 85 DEG C in temperature, reacts 20-30 minutes；Then stop heating, the pH in reaction kettle is adjusted with oxalic acid
Value is neutrality, and when being down to 40 DEG C or less at the temperature in reaction kettle, 2-3 parts of A151 silane coupling agents, tackifying resin 4-6 is added
Part stirring 20-30min, then filtering and discharging is to get to boron modified phenolic resin adhesive.
9. a kind of preparation method of high insulating property haloflex according to claim 1, it is characterised in that：It is described anti-
It is 1-2 that aging agent, which is phthalic acid with benzotriazole according to weight ratio,:1 composition.
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| CN101899124B (en) * | 2010-07-12 | 2011-12-28 | 杭州科利化工股份有限公司 | Preparation method of chlorinated polyethylene rubber with high insulation |
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