CN106008768A - High-efficiency production method of chlorinated polyethylene with high elongation - Google Patents
High-efficiency production method of chlorinated polyethylene with high elongation Download PDFInfo
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Abstract
The invention provides a high-efficiency production method of chlorinated polyethylene with a high elongation, and belongs to the technical field of production of chemical engineering assistants. The method comprises the following steps: 1, carrying out a chlorination reaction: introducing parts of chlorine to polyethylene at a temperature being lower than or equal to the melting point of polyethylene, carrying out the reaction, heating the reacted polyethylene to a temperature being 3DEG C or above higher than the melting point of polyethylene, introducing chlorine accounting for 55wt% or above of the total chlorine amount, and carrying out the chlorination reaction: 2, washing the obtained chlorination reaction product with water, and filtering the washed chlorination reaction product; 3, carrying out primary centrifuge: removing water from the above obtained water washing material through an acid-resistant centrifuge machine; 4, leaching: immersing a material obtained after the primary centrifuge in water in an acid-resistant container for 4h or above; 4, carrying out secondary centrifuge: removing water from the immersed material through the acid-resistant centrifuge machine; and 5, drying: drying the obtained material through an acid-resistant boiling drying bed. The method allows the chlorinated polyethylene with the elongation reaching 1300% or above to be obtained, and has the advantages of low production energy consumption and low preparation cost.
Description
[technical field]
The present invention relates to auxiliary chemicals production technical field, be specifically related to a kind of efficient production preparing high elongation rate chlorinated polyethylene
Method.
[background technology]
Chlorinated polyethylene (CPE) is a kind of macromolecular material, due to its good stability, excellent heat-resisting, ageing-resistant and
Fire resistance, is widely used in the fields such as plastics, rubber, building materials, electromechanics, automobile, military project, oneself become important production and
The material of life.Chlorinated polyethylene has two kinds of typical structures, and first chlorine atom is randomly uniformly distributed on macromolecular chain, becomes
For saturated elastomer；It two is chlorine atom random block distributed unevenly on macromolecular chain, shows the behavior of duroplasts.
The chlorinated polyethylene of chlorinty 25%-45% is a kind of heat-resisting, weathering and the specific rubber of resistance to combustion, has self-extinguishment.Chlorinty surpasses
The chlorinated polyethylene crossing 45% is white uniformity graininess amorphous solid.
Owing to chlorinated polyethylene (CPE) has caoutchouc elasticity, the impact strength of PVC can be improved, be widely used in without plasticising
The impact modification of PVC product.The most efficient method improving CPE impact strength is to improve the caoutchouc elasticity performance of CPE,
Caoutchouc elasticity performance is relevant with the elongation at break of rubber, and in general, elongation at break is the biggest, and the elastic performance of rubber is the best,
Then the shock resistance of CPE is the best.Research proves, the most uniform then its elongation at break that polyethylene is chlorinated is the biggest, and chlorine
The uniformity changed has close relationship with reaction process again.
The Chinese patent of Publication No. CN 100372874C discloses a kind of chlorinated polyethylene with high maximum elongation and preparation
Methods and applications, the method is after the following partial oxidation of fusing point of polyethylene, then the fusing point chlorine carried out above being warming up to polyethylene
Change reaction, the elongation at break the obtained high-elastic gonosome of chlorinated polyethylene more than 800%；This patent of invention also discloses: " 130 DEG C are arrived
The logical chlorine dose of 135 DEG C is the highest, and the elongation at break of obtained CPE is the highest, and the CPE that elongation at break is high simultaneously is modified
The impact strength of PVC is the highest ".But, the method is only limited to improve the chlorination reaction stage, in follow-up removing particle
The acid wrapped up, the operation remain the traditional deacidification of employing, neutralizing, wash and being dried, is a kind of the highest production of consuming energy
Mode.The CPE elongation at break using the method gained is the highest, also implies that CPE particle is the softest, in order to remove particle hole
The acid of the inside, neutralizes that institute is time-consuming and washing water consumption must be the most, neutralizes the time used and needs to increase to 18 hours, increases greatly
Add the energy consumption and time cost produced.If the acid within CPE is the most divisible, when being finally dried, product can turn to be yellow, product
Quality also can be affected.Therefore to control the energy consumption produced, it is ensured that the performance of product, the CPE prepared by this inventive embodiments
Percentage elongation be 800%-1200%, and the CPE of more high elongation rate can not be obtained.
[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 height preparing high elongation rate chlorinated polyethylene
Effect production method；With it, can obtain percentage elongation to reach the chlorinated polyethylene of more than 1300%, and the energy consumption produced is more
Low, manufacturing cost is lower.
To achieve these goals, the technical solution used in the present invention is as follows:
A kind of high-efficiency method for producing preparing high elongation rate chlorinated polyethylene, including the chlorination reaction carried out successively, washing filtering,
The step leaching, being centrifuged, be dried；Particularly as follows:
Described chlorination reaction is to be passed through after part chlorine reacts with water below the fusing point of polyethylene for suspension media, then heats up
It is passed through for more than 3 DEG C to the fusing point exceeding polyethylene and accounts for the chlorine of more than total logical chlorine dose 55wt.% and carry out chlorination reaction；
Described washing filtering be by chlorination reaction after material be cooled to less than 95 DEG C after be transferred in washing kettle, wash 1-2 with water
Secondary rear filtrate gets washing material；
Described leaching is to be soaked in water in acid-resistant container by described washing material, soaks more than 4 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.
Further, the step being the most just centrifuged after described washing filtering, before leaching, described being just centrifuged is that employing is acidproof
The moisture in the material after immersion sloughed by the centrifugal separator of property；Described leaching is that the material after being just centrifuged is soaked in water acidproof
In container, soak more than 3 hours.
Research shows, when the reaction temperature of chlorination reaction is relatively low, reaction can only be carried out at the particle surface of polyethylene, so poly-second
The chlorination uniformity of alkene is relatively low.Chlorination reaction temperature is the highest, particularly when the fusing point chlorination reaction carried out above of polyethylene, by
Can enter into the inside of melted polyethylene particle in chlorine, at this moment chlorination reaction is not only carried out on the surface of polyethylene also poly-
The inside of ethylene is carried out, so the chlorination of polyethylene is the most uniform, elongation at break and the shock resistance of the chlorinated polyethylene of synthesis are strong
Spend the highest.If but chlorination reaction is all carried out above at the fusing point of polyethylene, during the carrying out of chlorination reaction
There will be caking phenomenon, make production to be normally carried out.The present invention uses the method that chlorine is led in segmentation, below polyethylene fusing point first
Being passed through a part of chlorine, be passed through the chlorine accounting for more than total logical chlorine dose 55wt.% more than fusing point, during reaction, polyethylene can be chlorinated more
Uniformly.
But considering the reality produced, polyethylene can be chlorinated evenly, illustrates to react the kernel closer to polyethylene particle, raw
The hydrogen chloride become the most easily is trapped in kernel, and the difficulty of follow-up deacidification is bigger, if using traditional technique, soda boiling and washing
Time will be greatly increased, need time-consumingly to reach 18 hours, cause production cost to be greatly increased.
Therefore, the present invention has carried out technologic improvement to follow-up deacidification process, removes product surface initially with washing filtering
Floating acid and other impurity, the step for be not required to as tradition washing need washing more than 4-5 time, substantial amounts of water can be saved.
Material institute band moisture content can be removed through once centrifugal and remove floating acid further after washing.Certainly do not carry out the most centrifugal can also, but remove
The effect of acid can be slightly worse.Then by the way of being soaked in water, make the slow acid of chlorinated polyethylene inside particles discharge, pass
The method of system is to neutralize the acid of chlorinated polyethylene inside particles with alkali, for producing the product of high elongation rate, and the time used by soda boiling
Substantially will be more than 10 hours；And the present invention uses the mode of immersion, change into being made by infiltration by the method to inside fire attack dechlorinationization hydrogen
Discharge with making it.Due in production process of the present invention, chlorinated polyethylene material with a certain amount of acid, so the most centrifugal,
Secondary centrifuging and dry device therefor all use acid proof equipment, if the surface that centrifuge will contact with material in centrifuge
Material is transformed into acid resistant material, and the screen cloth being internally provided with is corrosion resistance, and titanium plate or zirconium plate can be used to make.Boiling
Rise drying bed and can use acid resistance fiberglass drying bed on the market, it would however also be possible to employ the applicant's independent research acidproof anti-quiet
The drying bed of electricity, and acidproof effect is more preferable, service life is longer.The baking temperature of boiling-bed drying typically more than 110 DEG C,
And hydrochloric acid is volatile material, can be divided in dry run, it is ensured that the quality of final products.Therefore, above-mentioned technology
Scheme is by technologic improvement and the improvement of equipment so that it is meet the Production requirement of band acid chlorinated polyethylene.It addition, on Shi Yonging
State production technology water consumption less and to need not use alkali raw material, produce a still (by 12 tons of calculation of capacity) chlorinated polyethylene than passing
System technique can be with using water wisely more than 20 tons, moreover it is possible to save the production time of 8-10 hour.
The Chinese patent of Publication No. CN100372874C uses the scheme of solution problem being more than fusing point that is 130 DEG C of polyethylene
Reaction temperature under be passed through the amount of chlorine and account for more than the 45% of total logical chlorine dose, so that the elongation at break of chlorinated polyethylene is more than
800%.But polyethylene is a kind of high molecular polymer, its fusing point can be divided into incipient melting, in molten and high melt temperature degree, less than 135 DEG C and also
It cannot be guaranteed that the kernel of polyethylene all melts, only when temperature is more than 136 DEG C, guarantee polyethylene particle all melts
Melt, make chlorination obtain evenly, so the present invention is when the 3rd section of logical chlorine, control temperature at 137 DEG C.
Thus, further improvement of the present invention also resides in the concrete step of described chlorination reaction and is:
(1) by the water of 800-900 weight portion, the polyethylene of 110-138 weight portion, the emulsifying agent of 0.15-0.25 weight portion and
The dispersant of 4-6.5 weight portion is put in reactor；
(2) add the initiator of 0.15-0.25 weight portion under agitation and be warming up to 70-80 DEG C and make sub polyethylene be dispersed in water
In, then heating to 110 DEG C, the chlorine being passed through total chlorine consumption 18-23wt.% in temperature-rise period carries out chlorination reaction；
(3) being warming up to 137 DEG C from 110 DEG C again, the chlorine being passed through total chlorine consumption 20-22wt.% in temperature-rise period carries out chlorination
Reaction；
(4) by temperature stabilization at 137 ± 0.5 DEG C, be passed through remaining chlorine and carry out chlorination reaction；
Wherein, total chlorine consumption is 1.15-1.2 times of polyethylene weight.
By promoting the temperature of reaction, the ventilation of the above chlorine of fusing point, the consumption of increase dispersant further, the present invention is permissible
Obtain average elongation at break chlorinated polyethylene product more than 1300%.
Further, described soak time controlled at 4-8 hour.The time soaked comes really according to the situation of chlorinated polyethylene particle
Fixed, for the chlorinated polyethylene product of high elongation rate, its particle is softer, and internal void is more, it is necessary to extend the time soaked.
Further, described polyethylene uses the Particle size requirements product less than 130 μm, it is preferred to use high density polyethylene (HDPE)
YEC-5305T, the polyethylene particle size of this trade mark is more tiny, is suitable for producing the chlorinated polyethylene product of high elongation rate.Polyethylene
Particle diameter the least, be more beneficial for the uniform of chlorination.
Further, described emulsifying agent is polyoxyethylene ether, detergent alkylate naphthenic acid sodium or stearic acid sodium；Dispersant is polyethylene
Ketopyrrolidine, methyl methacrylate.Described initiator be mass ratio be di-isopropylbenzene hydroperoxide and the peroxidating two of 1:4-8
Benzoyl.
In general, chlorinated polyethylene chlorination reaction, washing, homogenizing can use the equipment of liner enamel, but liner enamel
Service life of equipment short, and be easily damaged, uncomfortable be used as boiling-bed drying.Owing to producing, boiling-bed drying there is corrosion resistance
With the requirement of antistatic behaviour, the boiling-bed drying that present invention preferably uses is made up of fiberglass, including 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；Knot is strengthened in the middle of described
Structure layer is alternately to be covered bonding by glue with glass fabric to be composited；Described appearance aging resistance outer layer is by glue and aging resistance
Agent is to be injected in after centre strengthens structure sheaf surface after 100:2-3 mixes to solidify to form according to mass ratio；
Wherein said glue includes the raw material of following weight portion: vinylite 60-80 part, furfuryl alcohol resin 15-20 part, poly-different
Butylene 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, thickening
Resin 4-6 part.
Further, the manufacture method of described boron modified phenolic resin adhesive is: be ready to by weight phenol 90-110 part,
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, exists while stirring
Reactor adds barium hydroxide 3-5 part and aniline 2-3 part makees composite catalyst, stirs 15-20 minute；Then by reactor liter
Temperature reacts 50-60min to 75-80 DEG C；It is warming up to 85 DEG C again, adds the formaldehyde of remainder, react 20-30 minute；Then
Stop heating, be 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, add
Enter A151 silane coupler 2-3 part, tackifying resin 4-6 part stirring 20-30min, be then filtered off material, i.e. obtain boron modification
Synvaren.
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 resin, furan
Polyimide resin, polyisobutylene, sepiolite fibre, antistatic additive, firming agent, diluent resin, boron modified phenolic resin adhesive,
Part by weight between graphite powder, can make the overall corrosion resistance of drying bed, antistatic effect, resistance to elevated temperatures, intensity and
Toughness is satisfied by Production requirement.And its boron modification resin used is obtained by phenolic resin modified, there is viscosity high, viscous
Strong, the corrosion-resistant and resistant to elevated temperatures performance of knot property, it adds together with polyisobutylene and can have good amalgamation between each raw material,
Promote 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 that the method for the present invention uses segmentation to lead to chlorine carries out chlorination reaction, and the chlorinated polyethylene that can obtain high elongation rate produces
Product, by follow-up deacidification process has carried out the improvement of technique and equipment, greatly reduce energy consumption and the time cost of production,
It it is a kind of efficient production method.
2, the present invention is on the premise of technique carries out overall improvement, improves the temperature of polyreaction, strengthens the logical of the above chlorine of fusing point
Enter amount, increase the consumption of dispersant, the percentage elongation chlorinated polyethylene product more than more than 1300% can be obtained, same than on the market
Series products is softer, more bullet, more filling capacity.
3, boiling-bed drying is improved by the present invention, and the corrosion resistance of gained drying bed entirety is good, antistatic effect is strong, resistance to height
Warm nature good, the intensity of energy and toughness are satisfied by Production requirement.
[detailed description of the invention]
The present invention provides a kind of high-efficiency method for producing preparing high elongation rate chlorinated polyethylene, including chlorination reaction, washing filtering,
Leach, centrifugal, the step that is dried: described chlorination reaction is to be passed through after part chlorine reacts below the fusing point of polyethylene,
It is warming up to exceed the fusing point of polyethylene again be passed through for more than 3 DEG C and account for the chlorine of more than total logical chlorine dose 55wt.% and carry out chlorination reaction；Described
Washing filtering be by chlorination reaction after material be cooled to less than 95 DEG C after be transferred in washing kettle, leach after washing 1-2 time with water
Moisture must wash material；Described being once centrifuged is that the washing material acid proof centrifugal separator of employing is sloughed moisture；Described leaching
It is that washing material is soaked in water in acid-resistant container, soaks more than 4 hours；Described being centrifuged is to use acid proof centrifugation
The moisture in the material after immersion sloughed by machine；The described acid proof boiling-bed drying of dry employing.The method of the present invention uses segmentation
The method of logical chlorine carries out chlorination reaction, can obtain the chlorinated polyethylene product of high elongation rate, by carrying out follow-up deacidification process
The improvement of technique and equipment, greatly reduces energy consumption and the time cost of production, is a kind of efficient production method.
As some embodiments of the present invention, the step that described chlorination reaction is concrete is:
(1) by the water of 800-900 weight portion, the polyethylene of 110-138 weight portion, the emulsifying agent of 0.15-0.25 weight portion and
The dispersant of 4-6.5 weight portion is put in reactor；
(2) add the initiator of 0.15-0.25 weight portion under agitation and be warming up to 70-80 DEG C and make sub polyethylene be dispersed in water
In, then heating to 110 DEG C, the chlorine being passed through total chlorine consumption 18-23wt.% in temperature-rise period carries out chlorination reaction；
(3) being warming up to 137 DEG C from 110 DEG C again, the chlorine being passed through total chlorine consumption 20-22wt.% in temperature-rise period carries out chlorination
Reaction；
(4) by temperature stabilization at 137 ± 0.5 DEG C, be passed through remaining chlorine and carry out chlorination reaction；
Wherein, total chlorine consumption is 1.15-1.2 times of polyethylene weight.
As some embodiments of the present invention, described soak time controlled at 4-8 hour.
As some embodiments of the present invention, the Particle size requirements of described polyethylene is less than 130 μm, it is preferred to use be that high density is gathered
Ethylene YEC-5305T.The polyethylene particle size of this trade mark is more tiny, is suitable for producing the chlorinated polyethylene product of high elongation rate.
As some embodiments of the present invention, described emulsifying agent is polyoxyethylene ether, detergent alkylate naphthenic acid sodium or stearic acid sodium；
Dispersant is polyvinylpyrrolidone, methyl methacrylate.Described initiator be mass ratio be that the hydrogen peroxide two of 1:4-8 is different
Propyl benzene and dibenzoyl peroxide.
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.
One, production method embodiment
Embodiment 1
A kind of high-efficiency method for producing preparing high elongation rate chlorinated polyethylene, including chlorination reaction, washing filtering, once centrifugal,
Leaching, secondary centrifuging, dry step, particularly as follows:
The dispersant of the water of 800 weight portions, the polyethylene of 110 weight portions, the emulsifying agent of 0.15 weight portion and 4 weight portions is put
Enter in reactor；Add the initiator of 0.15 weight portion under agitation and be warming up to 70 DEG C and make polyethylene be dispersed in water,
Then heating to 110 DEG C, the chlorine being passed through total chlorine consumption 23wt.% in temperature-rise period carries out chlorination reaction；Rise from 110 DEG C again
Temperature is to 137 DEG C, and the chlorine being passed through total chlorine consumption 22wt.% in temperature-rise period carries out chlorination reaction；By temperature stabilization 137 ±
0.5 DEG C, it is passed through remaining chlorine and carries out chlorination reaction；Total chlorine consumption is 1.15 times of polyethylene weight, and the response time about 4 is little
Time.Emulsifying agent is polyoxyethylene ether and the detergent alkylate naphthenic acid sodium of 0.05 weight portion of 0.1 weight portion；Dispersant is 2 weight
The polyvinylpyrrolidone of part, 2 parts by weight of methylmethacrylate.Initiator be mass ratio be the hydrogen peroxide diisopropyl of 1:4
Benzene and dibenzoyl peroxide.
It is transferred in washing kettle after the material after chlorination reaction being cooled to below 95 DEG C by the way of chuck leads to cooling water, uses water
After washing 1 time, filtrate gets washing material；The washing material acid proof centrifugal separator of employing is sloughed moisture；Then by one
Secondary centrifugal after material be soaked in water in acid-resistant container, soak 4 hours；Acid proof centrifugal separator is used to slough immersion again
After material in moisture；Finally with acid proof boiling-bed drying by drying materials, while drying, hydrogen chloride all volatilizes
Come and be removed.
Embodiment 2
A kind of high-efficiency method for producing preparing high elongation rate chlorinated polyethylene, including chlorination reaction, washing filtering, once centrifugal,
Leaching, secondary centrifuging, dry step, particularly as follows:
By the water of 900 weight portions, the high density polyethylene (HDPE) of 138 weight portions, the emulsifying agent of 0.25 weight portion and 6.5 weight portions
Dispersant is put in reactor；Add the initiator of 0.25 weight portion under agitation and be warming up to 80 DEG C and make polyethylene disperse
In water, then heating to 110 DEG C, the chlorine being passed through total chlorine consumption 18wt.% in temperature-rise period carries out chlorination reaction；Again from
110 DEG C are warming up to 137 DEG C, and the chlorine being passed through total chlorine consumption 22wt.% in temperature-rise period carries out chlorination reaction；Temperature stabilization is existed
137 ± 0.5 DEG C, it is passed through remaining chlorine and carries out chlorination reaction；Total chlorine consumption is 1.2 times of polyethylene weight, and the response time is about
4 hours.Emulsifying agent is polyoxyethylene ether and the stearic acid sodium of 0.1 weight portion of 0.15 weight portion；Dispersant is 3 weight portions
Polyvinylpyrrolidone, 3.5 parts by weight of methylmethacrylate.Initiator be mass ratio be the di-isopropylbenzene hydroperoxide of 1:8
And dibenzoyl peroxide, the Particle size requirements of polyethylene is less than 130 μm.
It is transferred in washing kettle after the material after chlorination reaction being cooled to 90 DEG C by the way of chuck leads to cooling water, washes with water
After 2 times, filtrate gets washing material；The washing material acid proof centrifugal separator of employing is sloughed moisture；Then will once from
Material after the heart is soaked in water in acid-resistant container, soaks more than 6 hours；Acid proof centrifugal separator is used to slough immersion again
After material in moisture；Finally with acid proof boiling-bed drying by drying materials, while drying, hydrogen chloride all volatilizes
Come and be removed.
Embodiment 3
A kind of high-efficiency method for producing preparing high elongation rate chlorinated polyethylene, including chlorination reaction, washing filtering, leach, be centrifuged,
The step being dried, particularly as follows:
By the water of 900 weight portions, the high density polyethylene (HDPE) YEC-5305T of 125 weight portions, the emulsifying agent of 0.20 weight portion and 5
The dispersant of weight portion is put in reactor；Add the initiator of 0.20 weight portion under agitation and be warming up to 75 DEG C and make to gather
Ethylene is dispersed in water, and then heats to 110 DEG C, and being passed through the chlorine of total chlorine consumption 19wt.% in temperature-rise period, to carry out chlorination anti-
Should；Being warming up to 137 DEG C from 110 DEG C again, the chlorine being passed through total chlorine consumption 20wt.% in temperature-rise period carries out chlorination reaction；Will
Temperature stabilization, at 137 ± 0.5 DEG C, is passed through remaining chlorine and carries out chlorination reaction；Total chlorine consumption is 1.18 times of polyethylene weight,
About 4 hours response time.Emulsifying agent is polyoxyethylene ether and the detergent alkylate naphthenic acid sodium of 0.10 weight portion of 0.10 weight portion
Or stearic acid sodium；Dispersant is the polyvinylpyrrolidone of 3 weight portions, the methyl methacrylate of 2 weight portions.Initiator is
Mass ratio is di-isopropylbenzene hydroperoxide and the dibenzoyl peroxide of 1:6.
It is transferred in washing kettle after the material after chlorination reaction being cooled to 85 DEG C by the way of chuck leads to cooling water, washes with water
After 2 times, filtrate gets washing material；Washing material is soaked in water in acid-resistant container, soaks 8 hours；Use acidproof again
The moisture in the material after immersion sloughed by the centrifugal separator of property；Finally with acid proof boiling-bed drying by drying materials, dry
While, hydrogen chloride all evaporates and is removed.
Chlorinated polyethylene obtained in embodiment 1-3, uses the side that HG/T2704-2010 chlorinated polyethylene industry standard is recorded
Method carries 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 national standard, and
The elongation at break of product, more than 1300%, has the elongation at break of superelevation.
Embodiment 1-3 and traditional technique (chlorination-deacidification-neutralization-except alkali-centrifugal-be dried) compared with, water consumption is less, produces
One still (by 12 tons of calculation of capacity) chlorinated polyethylene can be with using water wisely more than 20 tons than traditional handicraft, moreover it is possible to save 8-10 little
Time production time.
Two, boiling-bed drying embodiment
Embodiment 4
The acid resistance anlistatig fiberglass boiling-bed drying prepared by the following method, is particularly suitable for applying in the present invention.Its
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 phenol 90 by weight
Part, 20 parts of formaldehyde, Firebrake ZB 5 parts, barium hydroxide 3 parts, aniline 2 parts, A151 silane coupler 2 parts, tackifying resin
EVA 4 parts；Phenol 90 parts, 5 parts of formaldehyde and Firebrake ZB 5 parts are joined in reactor, adds hydrogen at reactor while stirring
Barium monoxide 3 parts 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 DEG C again, adds the formaldehyde of remainder, react 20 minutes；Then heating is stopped, with in oxalic acid regulation reactor
PH value be neutral, in question response still at a temperature of when being down to less than 40 DEG C, add A151 silane coupler 2 parts, thickening is set
Fat SBS 4 parts stirs 20min, is then filtered off material, i.e. obtains boron modified phenolic resin adhesive.Gained boron modification phenolic aldehyde tree
The free phenol of fat adhesive 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
Diluent diluent resin is expoxy propane o-cresyl ether 15 parts, boron modified phenolic resin adhesive 6 parts, graphite powder 0.5 part；
Stir 5min with high speed dispersor with the linear velocity of 15m/s, obtain glue.Glue is pressed the demand of internal layer, intermediate layer and outer layer
Amount is divided into 3 parts, and respectively internal layer glue, intermediate layer glue and outer layer glue, according to glue and age resister in outer layers glue
Mass ratio be that 100:2 mix homogeneously is standby, wherein, age resister is phthalic acid and benzotriazole is 1:1 according to weight ratio
Composition.
(3) using the mode of injection to make drying bed anticorrosion internal layer, the thickness of internal layer is 0.5mm-2mm, and the present embodiment is
1mm；Then intermediate layer glue is put in maceration tank, after hose lining liquid-solidization, use and be wound around unit, with glass fabric one
The mode of limit dipping glue Stagger-wrap on one side is fabricated to middle enhancing structure sheaf；Structure sheaf surface injection one is finally strengthened in centre
Layer glue and ageing-resistant mixture, form appearance aging resistance outer layer after cured, and the thickness of outer layer is 0.5mm-2mm,
The present embodiment is 1mm.
Embodiment 5
The acid resistance anlistatig fiberglass boiling-bed drying prepared by the following method, is particularly suitable for applying in the present invention.Its
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 phenol 110 by weight
Part, 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 at reactor while stirring
Barium hydroxide 5 parts and aniline 3 parts make composite catalyst, stir 20 minutes；Then reactor is warming up to 80 DEG C of reaction 50min；
It is warming up to 85 DEG C again, adds the formaldehyde of remainder, react 30 minutes；Then heating is stopped, with in oxalic acid regulation reactor
PH value be neutral, in question response still at a temperature of when being down to less than 40 DEG C, add A151 silane coupler 3 parts, thickening is set
6 parts of fat stirring 30min, is then filtered off material, i.e. obtains boron modified phenolic resin adhesive.Gained boron modified phenolic resin glue
The free phenol of stick 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
Diluent 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 internal layer, intermediate layer and outer layer
Demand is divided into 3 parts, respectively internal layer glue, intermediate layer glue and outer layer glue, according to glue with anti-ageing in outer layers glue
The mass ratio of agent is that 100:3 mix homogeneously is standby, and wherein, age resister is that phthalic acid is according to weight ratio with benzotriazole
2:1 forms.
(3) using the mode of injection to make drying bed anticorrosion internal layer, the thickness of internal layer is 0.5mm-2mm；Then by centre
Layer glue is put in maceration tank, after hose lining liquid-solidization, use and is wound around unit, impregnate glue with glass fabric
The mode of Stagger-wrap is fabricated to middle enhancing structure sheaf；Structure sheaf surface one layer of glue of injection and aging resistance is finally strengthened in centre
The mixture of agent, forms appearance aging resistance outer layer after cured.
In embodiment 4-5, the indices of obtained fiberglass drying bed is the most different, and volumetric resistivity value is about 108Ω cm,
Meet anlistatig demand.Corrosion resistance test is carried out over 20 days, in dried material with the soak with hydrochloric acid of 25% high concentration
Concentration of hydrochloric acid, result of the test is that fiberglass does not has significant change, it was demonstrated that it has good acid-resistant corrosion.Additionally its intensity
The demand of actual production is all met with toughness.
Described above is the detailed description for the preferable possible embodiments of the present invention, but embodiment is not limited to the special of the present invention
Profit application range, the equal change completed under the technical spirit suggested by all present invention or modification change, the present invention all should be belonged to
Contained the scope of the claims.
Claims (10)
1. the high-efficiency method for producing preparing high elongation rate chlorinated polyethylene, it is characterised in that: include that the chlorination carried out successively is anti-
Should, washing filtering, leach, be centrifuged, dry step；Particularly as follows:
Described chlorination reaction is to be passed through after part chlorine reacts with water below the fusing point of polyethylene for suspension media, then heats up
It is passed through for more than 3 DEG C to the fusing point exceeding polyethylene and accounts for the chlorine of more than total logical chlorine dose 55wt.% and carry out chlorination reaction；
Described washing filtering be by chlorination reaction after material be cooled to less than 95 DEG C after be transferred in washing kettle, wash 1-2 with water
Secondary rear filtrate gets washing material；
Described leaching is to be soaked in water in acid-resistant container by described washing material, soaks more than 4 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.
A kind of high-efficiency method for producing preparing high elongation rate chlorinated polyethylene the most according to claim 1, it is characterised in that:
Also having the most centrifugal step after described washing filtering, before leaching, described being just centrifuged is to use acid proof centrifugal separator
Slough the moisture in the material after immersion；Described leaching is that the material after being just centrifuged is soaked in water in acid-resistant container, soaks 3
More than hour.
A kind of high-efficiency method for producing preparing high elongation rate chlorinated polyethylene the most according to claim 1 and 2, its feature exists
In: the step that described chlorination reaction is concrete is:
(1) by the water of 800-900 weight portion, the polyethylene of 110-138 weight portion, the emulsifying agent of 0.15-0.25 weight portion and 4-6.5
The dispersant of weight portion is put in reactor；
(2) add the initiator of 0.15-0.25 weight portion under agitation and be warming up to 70-80 DEG C and make sub polyethylene be dispersed in water
In, then heating to 110 DEG C, the chlorine being passed through total chlorine consumption 18-23wt.% in temperature-rise period carries out chlorination reaction；
(3) being warming up to 137 DEG C from 110 DEG C again, being passed through the chlorine of total chlorine consumption 20-22wt.% in temperature-rise period, to carry out chlorination anti-
Should；
(4) by temperature stabilization at 137 ± 0.5 DEG C, be passed through remaining chlorine and carry out chlorination reaction；
Wherein, total chlorine consumption is 1.15-1.2 times of polyethylene weight.
A kind of high-efficiency method for producing preparing high elongation rate chlorinated polyethylene the most according to claim 1, it is characterised in that:
Described soak time controlled at 4-8 hour.
A kind of high-efficiency method for producing preparing high elongation rate chlorinated polyethylene the most according to claim 1 and 2, its feature exists
In: the Particle size requirements of described polyethylene is less than 130 μm.
A kind of high-efficiency method for producing preparing high elongation rate chlorinated polyethylene the most according to claim 2, it is characterised in that:
Described emulsifying agent is polyoxyethylene ether, detergent alkylate naphthenic acid sodium or stearic acid sodium；Dispersant is polyvinylpyrrolidone, methyl
Acrylic acid methyl ester..
A kind of high-efficiency method for producing preparing high elongation rate chlorinated polyethylene the most according to claim 2, it is characterised in that:
Described initiator be mass ratio be di-isopropylbenzene hydroperoxide and the dibenzoyl peroxide of 1:4-8.
A kind of high-efficiency method for producing preparing high elongation rate chlorinated polyethylene the most according to claim 1 and 2, its feature exists
In: described boiling-bed drying includes anticorrosion internal layer, middle enhancing structure sheaf and appearance aging resistance outer layer；Described anticorrosion internal layer is by glue
Liquid solidify to form after being injected on mould；It is compound with glass fabric alternately covering bonding by glue for strengthening structure sheaf in the middle of described
Form；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-different
Butylene 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, thickening
Resin 4-6 part.
A kind of high-efficiency method for producing preparing high elongation rate chlorinated polyethylene the most according to claim 8, it is characterised in that:
The manufacture method of described boron modified phenolic resin adhesive is: be ready to by weight phenol 90-110 part, formaldehyde 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；
Phenol 90-110 part, formaldehyde 5-8 part and Firebrake ZB 5-8 part are joined in reactor, adds hydrogen-oxygen at reactor while stirring
Change barium 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 instead
Answer 50-60min；It is warming up to 85 DEG C again, adds the formaldehyde of remainder, react 20-30 minute；Then heating is stopped, with grass
PH value in acid regulation reactor be neutral, in question response still at a temperature of when being down to less than 40 DEG C, A151 is silane coupled in addition
Agent 2-3 part, tackifying resin 4-6 part stirring 20-30min, be then filtered off material, i.e. obtain boron modified phenolic resin adhesive.
A kind of high-efficiency method for producing preparing high elongation rate chlorinated polyethylene the most according to claim 8, 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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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103224674A (en) * | 2013-05-09 | 2013-07-31 | 山东日科化学股份有限公司 | Polyvinyl chloride modifier, polyvinyl chloride composition and preparation method of polyvinyl chloride composition |
-
2016
- 2016-05-30 CN CN201610372564.7A patent/CN106008768A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103224674A (en) * | 2013-05-09 | 2013-07-31 | 山东日科化学股份有限公司 | Polyvinyl chloride modifier, polyvinyl chloride composition and preparation method of polyvinyl chloride composition |
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