CN101665555A - Method for preparing continuous bulk of flame retardant and highly impact resistant acrylonitrile-chlorinated polyethylene-styrene resin - Google Patents
Method for preparing continuous bulk of flame retardant and highly impact resistant acrylonitrile-chlorinated polyethylene-styrene resin Download PDFInfo
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Abstract
A method for preparing a continuous bulk of a flame retardant and highly impact resistant acrylonitrile-chlorinated polyethylene-styrene resin comprises the following steps: dissolving chlorinated polyethylene rubbers, butadiene rubbers, flame retardants and auxiliaries into a mixture of mono alkyl ethylene aromatic monomers and unsaturated nitrile monomers to be involved in polymerization reaction as first feed solution, mixing the first feed solution with second feed, containing the same or different flame retardants, of mixed solution of aromatic hydrocarbon and with additive feed, containing heat stabilizers and lubricants, of the mixed solution of aromatic hydrocarbon, and then continuously carrying out polymerization reaction. The resin prepared by the method of the invention has high notch impact strength, high flame retardant rating, superior comprehensive performance and excellent antistatic performance and weather resistance. The volume resistivity can reach 2.0*10<12> and below, and the notch impact strength retention rate can reach 70% and above under the condition of artificial weathering for more than 1000h; therefore, the resin can be on a par with the ASA resins famous for weather resistance.
Description
Technical field
The present invention relates to the preparation field of macromolecule chemical material, relate in particular to the method for preparing continuous bulk of a kind of flame retardant and highly impact resistant acrylonitrile-chlorinatedpolyethylene-styrene resin.
Background technology
Acrylonitrile-chloride polyethylene-styrene resin is a kind of thermoplastic resin that has vinyl cyanide, chlorinatedpolyethylene and styrene-grafted to be polymerized, and is in order to remedy the not enough and macromolecular material of an excellent property being born of performances such as ABS resin flame retardant resistance, weathering resistance, static resistance.Acrylonitrile-chloride polyethylene-styrene resin is pressed its preparation method, can be divided into graft type and mixed type two big classes, and wherein graft type can be divided into two kinds of substance law and water methods by the grafted method; By its use properties, can be divided into coventional type, flame retardant type and transparent type etc. again.Acrylonitrile-chloride polyethylene-styrene resin adopts halogen-containing saturated elastomerics-chlorinated polyethylene rubber (CPE) to replace polybutadiene rubber, not only keep ABS resin inherent good physical and mechanical property, electric property and chemical property etc., also improved flame retardant resistance, weathering resistance, heat-resistant aging and the antistatic property of resin.But the common acrylonitrile-chloride polyethylene-styrene resin of preparation himself does not have higher flame retardant properties, need carry out chemistry and physically modified, improve its flame retardant rating, use temperature and physical and mechanical property etc., and can carry out modification according to different application conditions, satisfy the demand in many-sided different markets.
Acrylonitrile-chloride polyethylene-styrene resin was at first developed in 1961 with Electrical Appliance Industry Company by Japan is clear, applied for graft type resin patent, applied for the hybrid resin patent again, set up pilot plant, put into serial production in 1977 years in 1966 in 1966 in 1964.At present, acrylonitrile-chloride polyethylene-styrene resin as a kind of performance resins of the said firm in market sale.Aspect modified propylene nitrile-chlorinatedpolyethylene-styrene resin, Japan is clear to have produced acrylonitrile-chloride polyethylene-styrene resins such as flame retardant type, transparent type with Electrical Appliance Industry Company, by in acrylonitrile-chloride polyethylene-styrene resin, adding the polyamide-based resin and the halogen flame of suitable fusing point, and add antimonous oxide as required, adopt mechanical mixing to make physical and mechanical property and all good flame retardant type acrylonitrile-chloride polyethylene-styrene resins that gets of flame retardant properties.In addition, many major companies all developed acrylonitrile-chloride polyethylene-styrene resin in succession since the sixties, the important tendency of these companies research be improve the transparency of acrylonitrile-chloride polyethylene-styrene resin, the performance of spraying paint and with acrylonitrile-chloride polyethylene-styrene resin as the properties-correcting agent of polyvinyl chloride (PVC) RESINS etc.
Chinese patent literature CN1587290A has disclosed the preparation method of a kind of acrylonitrile-chloride polyethylene-styrene resin water-phase grafting copolymerization, but it adopts water method technology, process complexity, big, seriously polluted, the product foreign matter content height of water treatment amount.Chinese patent literature CN101058621A has disclosed a kind of preparation method of continuous bulk graft copolymerization of acrylonitrile-chloride polyethylene-styrene resin, but this method technological process relative complex, facility investment is big, the resin of preparation need just can reach the flame retardant rating requirement by certain modified method, and easy high-temperature discoloration in the preparation process.Acrylonitrile-chloride polyethylene-the styrene resin of Chinese patent literature CN101058621A preparation is because the restriction of its shock resistance, be suitable for using as general general engineering plastic, higher in shock resistance, particularly be subjected to bigger restriction on the Application Areas that low-temperature impact resistance is had relatively high expectations.
Summary of the invention
The objective of the invention is to avoid the defective of prior art, provide that a kind of preparation technology is reasonable in design, the method for preparing continuous bulk of physical and mechanical property and flame retardant and highly impact resistant acrylonitrile-chlorinatedpolyethylene-styrene resin that processing characteristics is good, weathering resistance and static resistance are good.
Purpose of the present invention is achieved through the following technical solutions:
The method for preparing continuous bulk of a kind of flame retardant and highly impact resistant acrylonitrile-chlorinatedpolyethylene-styrene resin comprises:
1. rubber is dissolved in the mixing solutions of monoalkyl vinyl aromatic monomer, unsaturated nitrile monomer and solvent, mix the back with fire retardant, initiator, chain-transfer agent, oxidation inhibitor and form rubber solutions, enter first reactor as first charging and carry out graft polymerization reaction; Wherein, described rubber is the combination of chlorinated polyethylene rubber and butadiene type rubber, chlorinated polyethylene rubber weight average particle diameter 0.3-0.8 micron, butadiene type rubber weight average particle diameter 1.0-5.0 micron.
First charging polyreaction solids content to the polymerisate in first reactor is 35-55%, and first feed rate is 800-1500ml/h, and temperature of reaction is 100-125 ℃, and reaction pressure is 0.3-1.0Mpa, and stirring velocity is 40-160 rev/min.
Wherein, described chlorinated polyethylene rubber molecular weight is 100,000-250, and 000, the chlorine weight percentage is 20-45%; Preferably, described chlorinated polyethylene rubber molecular weight is 120,000-200, and 000, the chlorine weight percentage is 35-42%.
Described butadiene type rubber is preferably one or more of following substances: low-cis-polybutadiene rubber, cis-rich polybutadiene rubber, butadiene-styrene block copolymer, described butadiene type molecular weight rubber is 150,000-350,000, preferably, described butadiene type molecular weight rubber is 200,000-300,000.
Described monoalkyl vinyl aromatic monomer is preferably one or more in the following substances: vinylbenzene, alpha-methyl styrene, α-ethyl styrene, neighbour-,-and p-methylstyrene, 2,4-dimethyl styrene, right-t-butyl styrene, α-ethyl p-methylstyrene, neighbour-,-and right-chloro-styrene, neighbour-bromstyrol, 2,4-Dowspray 9,2-methyl-4-chloro-styrene, 2,6-two chloro-4-vinyl toluenes; Vinylbenzene more preferably.
Described unsaturated nitrile monomer is preferably and is one or more of following substances: vinyl cyanide, Alpha-Methyl vinyl cyanide, ethyl acrylonitrile; Vinyl cyanide more preferably.
Described solvent is preferably and is aliphatic ketone and/or aromatic hydrocarbon, and wherein, described aliphatic ketone is preferably one or more in acetone, methyl ethyl ketone, the methyl propyl ketone, and described aromatic hydrocarbon is preferably one or more in benzene, toluene, the ethylbenzene; More preferably acetone and/or ethylbenzene.
The described first charging fire retardant is preferably one or more of following substances: the tetrabromo-bisphenol diphenyl phosphoester, the two phenyl phosphate ester (RDP) of Resorcinol, the tetrabromo-phthalate glycol, tricresyl phosphate (2-chloroethyl) ester, triaryl phosphate, the cyclisation phosphoric acid ester, clorafin, close the halogen polyether glycol, tetrabromo-bisphenol, the tetrabromo-bisphenol epoxy oligomer, brominated Polystyrene, 1,2-two (2,4, the 6-tribromophenoxy) ethane, the two tetrabromo phthalimides of ethylene, decabrominated dipheny base ethane, decabromodiphenyl oxide, antimony tetroxide, antimonous oxide, tellurium dioxide; More preferably two phenyl phosphate ester (RDP), tetrabromo-phthalate glycol, tricresyl phosphate (2-chloroethyl) ester, triaryl phosphate, cyclisation phosphoric acid ester, clorafins of tetrabromo-bisphenol diphenyl phosphoester, Resorcinol, close halogen polyether glycol, decabrominated dipheny base ethane.
Described initiator is preferably one or more of following substances: t-butyl perbenzoate, sec.-propyl percarbonic acid tertiary butyl ester, cross sad tertiary butyl ester, cross different n-nonanoic acid tertiary butyl ester, 2-ethylhexyl list peroxide carbonic acid tertiary butyl ester, cross the neodecanoic acid tertiary butyl ester.
Described chain-transfer agent is preferably and is in linear dimer, n-butyl mercaptan, tert-butyl mercaptan, octyl mercaptan, the lauryl mercaptan one or more.
Gross weight in the first charging rubber solutions is 100%,
Described monoalkyl vinyl aromatic monomer content is 37-53%;
Described unsaturated nitrile monomer content is 12-18%;
Described chlorinated polyethylene rubber content is 8-16%;
Described butadiene type rubber content is 1-5%;
Described weight of solvent is 10-30%;
The described first charging flame retardant agent content is 0-8%;
Described initiator weight is 0.03-0.2%;
Described chain-transfer agent weight is 0.2-0.8%;
Described oxidation inhibitor weight is 0.2-0.6%.
2. with the polymerisate of first charging in first reactor in the described step 1, with second charging of the aromatic hydrocarbon mixing solutions that contains fire retardant with contain the additive charging thorough mixing of the aromatic hydrocarbon mixing solutions of thermo-stabilizer, lubricant, enter second reactor, proceed graft polymerization reaction and particle-stabilised, rubber weight average particle diameter 0.3-1.2 micron.
First charging polyreaction solids content to the polymerisate in second reactor is 55-80%, and temperature of reaction is 125-155 ℃, and reaction pressure is 0.3-1.0Mpa, and stirring velocity is 20-70 rev/min.
Second charging and additive feed rate are 50-200ml/h, and stirring velocity is 30-100 rev/min.
Described aromatic hydrocarbon is preferably and is in benzene, toluene, the ethylbenzene one or more, more preferably ethylbenzene.
The described second charging fire retardant is preferably one or more of following substances: the tetrabromo-bisphenol diphenyl phosphoester, the two phenyl phosphate ester (RDP) of Resorcinol, the tetrabromo-phthalate glycol, tricresyl phosphate (2-chloroethyl) ester, triaryl phosphate, the cyclisation phosphoric acid ester, clorafin, close the halogen polyether glycol, tetrabromo-bisphenol, the tetrabromo-bisphenol epoxy oligomer, brominated Polystyrene, 1,2-two (2,4, the 6-tribromophenoxy) ethane, the two tetrabromo phthalimides of ethylene, decabrominated dipheny base ethane, decabromodiphenyl oxide, antimony tetroxide, antimonous oxide, tellurium dioxide; More preferably two phenyl phosphate ester (RDP), tetrabromo-phthalate glycol, tricresyl phosphate (2-chloroethyl) ester, triaryl phosphate, cyclisation phosphoric acid ester, clorafins of tetrabromo-bisphenol diphenyl phosphoester, Resorcinol, close halogen polyether glycol, decabrominated dipheny base ethane.
Described thermo-stabilizer is one or more in the following substances: dibutyl tin laurate, toxilic acid dibutyl tin, lauric acid toxilic acid dibutyl tin, thiol methyl tin, mercaptan trioctylphosphine tin, barium/cadmium carboxylate stabilizer, barium/zinc composite stabilizer, calcium/zinc composite stabilizer, calcium stearate, Zinic stearas, lead sulfate tribasic, second base lead sulfate; More preferably dibutyl tin laurate and/or toxilic acid dibutyl tin and/or lauric acid toxilic acid dibutyl tin and/or thiol methyl tin and/or mercaptan trioctylphosphine tin.
Described lubricant is one or more in the following substances: paraffin, polyethylene wax, Zerol, stearyl alcohol, pentaerythritol ester, stearic amide, erucicamide, ethylene bis stearamide, Zinic stearas; More preferably polyethylene wax, Zerol, pentaerythritol ester, ethylene bis stearamide.
Gross weight in the first charging rubber solutions is 100%,
The add-on of the described second charging fire retardant is 2-10%;
The add-on of described thermo-stabilizer is 0.2-1.5%;
The add-on of described lubricant is 0.3-1.6%.
3. will be from the material of second reactor discharge, separate through the secondary devolatilization, extruding pelletization, obtain flame retardant and highly impact resistant acrylonitrile-chlorinatedpolyethylene-styrene resin, rubber weight average particle diameter 0.3-1.0 micron wherein, rubber content is 15-30%, and the vertical combustion grade is V-0 or V-1, monomer conversion 75-95%.
One-level devolatilizer temperature is 160-180 ℃, and one-level devolatilizer pressure is absolute pressure 101-120kpa; Secondary devolatilizer temperature is 200-220 ℃, and secondary devolatilizer pressure is absolute pressure 1-20kpa.
In preparation method of the present invention, add initiator, chain-transfer agent, fire retardant, oxidation inhibitor in the step 1, more preferably, in step 1, add the preferable oxidation inhibitor of dissolution dispersity, to obtain rosin products good antioxidant property in the high temperature devolatilizer, guarantee that product has preferable outward appearance and color and luster.
For the fire retardant of introducing in the step 1, we expect that it has dispersiveness, solvability and high-temperature stability preferably, and changing for the unpredictable chemical that takes place is that we need avoid and control as possible.Though the fire retardant of introducing in the step 1 has greatly improved the flame retardant properties of rosin products easily on technology and technology, but the usage quantity of fire retardant should be controlled, because the existence of a large amount of fire retardants, make the formation of polyreaction in the polymerization process, graft reaction, rubber particles and distribution etc. all can be subjected to influence to a certain extent.For this reason, we introduce the second charging fire retardant by step 2, later stage at whole polymerization process is introduced fire retardant, to reduce the negative property influence of the first charging fire retardant to entire reaction course, also the flame retardant properties of rosin products is brought up to our desired flame retardant rating simultaneously.
In preparation method of the present invention, we have carried out more excellent selection to chlorinated polyethylene rubber, though chlorinated polyethylene rubber has outstanding physical and mechanical property equally with respect to butadiene type rubber, but because of being subjected to preparation technology and technical restriction, acrylonitrile-chloride polyethylene-styrene resin the fat prod that fully only uses chlorinated polyethylene rubber preparation is with respect to ABS resin still gap slightly on shock resistance, but obtained bigger raising on flame retardant resistance, static resistance and weathering resistance.We have optionally added a spot of butadiene type rubber, the interpolation of butadiene type rubber, rosin products there is to a certain degree negative impact in flame retardant resistance, static resistance and weathering resistance, because after butadiene type rubber adds, chlorine weight percentage in the rosin products reduces relatively, has reduced its flame retardant resistance; Nonpolar linkage in the rosin products and group increase, and have reduced its static resistance; Unsaturated group mass contg in the rosin products increases, and has reduced its weathering resistance.But because just a small amount of add and by the improvement on the Technology, this influence does not make these performance impacts demonstrate evident difference, on the contrary, the interpolation of butadiene type rubber makes that the rubber size of rosin products and distribution are excellent more, present certain bimodal distribution, and making rosin products on shock resistance, obtain bigger raising, such result remains that we are desired and pursue.
Because the difference of raw material on molecular weight, molecular chain length, the degree of branching of preparation chlorinated polyethylene rubber causes and adopts the rosin products of chlorinated polyethylene rubber preparation to show relatively poor on processing flowability.By the additive charging, improved the processing fluidity of product preferably, simultaneously, the thermo-stabilizer of interpolation has not only improved rosin products thermal stability at high temperature, and the processing characteristics of rosin products is also increased.
The present invention only uses two reactors, has omitted pre-polymerization reactor, has simplified preparation process, has not only reduced equipment cost, also makes whole process of preparation convenient in control.By rational technology controlling and process, two reactors can have been realized three reactors, even more the functions that reactor can be realized.
Acrylonitrile-chloride polyethylene-styrene resin fat prod by preparation method's manufacturing of the present invention, when having high socle girder breach resistance to impact shock, high flame retardant rating, guarantee that again it possesses good weathering resistance, static resistance simultaneously, over-all properties is superior.Adopt the vertical combustion method of GB/T 2408 bioassay standards can reach V-1 and V-0 rank, adopt GB/T1410 bioassay standard volume specific resistance can reach 2.0 * 10
12And below, artificial weathering more than 1000 hours product socle girder breach resistance to impact shock conservation rate reach 70% and more than, can reach anti-marquis's grade of ASA resin substantially.
By acrylonitrile-chloride polyethylene-styrene resin fat prod that preparation method of the present invention makes, can be applicable to fire-retardant, anti-marquis, the material field that requires such as antistatic, be applicable to and make office machine shell and parts; Household appliances shell and part; Electric switch, joint; Communication Instrument, equipment, communication component; Building and ornament materials; Wrapping material; Automobile component; Product such as fire-protection device and assembly.
Description of drawings
Fig. 1 the method for the invention process flow sheet.
Embodiment
Embodiment 1:
In the glue pot that nitrogen purging is crossed, add ethylbenzene, vinylbenzene, vinyl cyanide, extra large brilliant CPE135, AsiaSat CPE2135,35AE rubber, cross sad tertiary butyl ester, antioxidant 1076, lauryl mercaptan, tricresyl phosphate (2-chloroethyl) ester according to the parts by weight in the table 1, dissolving is stirred, and the raw material glue entered in two placed in-line tower reactors after colloidal sol was finished.In second charging stock tank, add ethylbenzene and tricresyl phosphate (2-chloroethyl) ester, fully stirring and dissolving.In the additive charging stock tank, add thiol methyl tin and ethylene bis stearamide, fully mix.
Carry out successive polymerization reaction according to condition in the table 1 and the described technical process of Fig. 1, the polymerisate of generation through devolatilization, extrude, step such as granulation obtains the rosin products particle.
Table 1
The rosin products that obtains is measured socle girder breach resistance to impact shock and 1000h artificial weathering socle girder breach shock resistance conservation rate by GB/T1843; Press GB/T1040 and measure tensile break strength and elongation at break; Press GB/T2408 and measure the vertical combustion grade; Press GB/T1410 and measure volume specific resistance.Measurement result is as shown in table 2.
Determination data from table 2 can be seen, after adding butadiene type rubber and in first charging and second charging, adding fire retardant, the rosin products that obtains has high breach resistance to impact shock and high flame retardant rating, and antistatic property and weather resistance are good.
Table 2
Embodiment 2 and 3:
In the glue pot that nitrogen purging is crossed, add ethylbenzene, vinylbenzene, vinyl cyanide, the sharp CPE135B of section, 35AE rubber, cross neodecanoic acid tertiary butyl ester, antioxidant 1010, linear dimer, triaryl phosphate according to the parts by weight in the table 1, dissolving is stirred, and the raw material glue entered in two placed in-line tower reactors after colloidal sol was finished.In second charging stock tank, add ethylbenzene and triaryl phosphate, fully stirring and dissolving.In the additive charging stock tank, add dibutyl tin laurate and polyethylene wax, fully mix.
Carry out successive polymerization reaction according to the condition in the table 1, the polymerisate of generation through devolatilization, extrude, step such as granulation obtains the rosin products particle.Measure according to the same procedure among the embodiment 1, the result is as shown in table 2.
Determination data from table 2 can be seen, increase gradually along with butadiene type rubber usage quantity among the embodiment 1,2,3, the breach shock resistance of rosin products improves gradually, but, in the breach shock resistance raising to rosin products certain influence is arranged because styrene content increases in embodiment 2 and 3 rubber solutions.Along with the increase of divinyl rubber usage quantity, rosin products slightly descends on antistatic property and weather resistance, but amplitude is little.
Embodiment 4:
Add various raw materials according to the step among the embodiment 1, wherein chlorinated polyethylene rubber is the sharp CM402 of section, and butadiene type rubber is SBR rubber, and initiator is a t-butyl perbenzoate, and thermo-stabilizer is a thiol methyl tin, and all the other raw materials are all identical with embodiment 1.The rosin products that obtains is measured according to method identical among the embodiment 1, and the result is as shown in table 2.
Determination data from table 2 can see, is 42% the sharp CM402 of section owing to used the chlorine weight percentage, and therefore under the situation that the second charging fire retardant usage quantity reduces, rosin products still can obtain desired flame retardant rating.In embodiment 4, we have improved the usage quantity of thermo-stabilizer, and have suitably reduced the devolatilization temperature of devolatilizer, to guarantee the thermostability of product.
In embodiment 4, we have used SBR rubber, because the difference between the butadiene type rubber increases among the relative embodiment 1 of the physical and mechanical property of rosin products, still the influence on antistatic property and weather resistance is still little.
Embodiment 5:
Add various raw materials according to the step among the embodiment 1, wherein the first charging fire retardant does not use, and butadiene type rubber is 35AE rubber, and the second charging fire retardant is a triaryl phosphate, and all the other raw materials are all identical with embodiment 1.The rosin products that obtains is measured according to method identical among the embodiment 1, and the result is as shown in table 2.
Determination data from table 2 can be seen, butadiene type rubber comparative example 3 increases, but because the decline of chlorinated polyethylene rubber usage quantity, it is not very big that the shock resistance of rosin products improves, but owing to do not add the first charging fire retardant, the relative embodiment 3 of the physical and mechanical property of rosin products has relatively large raising.
Embodiment 6:
Add various raw materials according to the step among the embodiment 1, wherein chlorinated polyethylene rubber is the sharp CM402 of section, and butadiene type rubber is SBR rubber, and initiator was different n-nonanoic acid tertiary butyl ester, and thermo-stabilizer is a dibutyl tin laurate, and all the other raw materials are all identical with embodiment 1.The rosin products that obtains is measured according to method identical among the embodiment 1, and the result is as shown in table 2.
Determination data from table 2 can see, the chlorine weight percentage is that the relative embodiment 4 of usage quantity of 42% the sharp CM402 of section increases to some extent, and the while, employed SBR rubber usage quantity also increased, so the breach resistance to impact shock of rosin products has bigger lifting.Though the usage quantity of the second charging fire retardant is less, because the increase of the sharp CM402 usage quantity of section, rosin products has still reached the flame retardant rating of V-0.And owing to do not add the first charging fire retardant, the physical and mechanical property of rosin products is also more excellent relatively.
Embodiment 7:
Add various raw materials according to the step among the embodiment 1, wherein chlorinated polyethylene rubber is extra large brilliant CPE135A, butadiene type rubber is the mixed rubber of 35AE rubber and SBR rubber, initiator was different n-nonanoic acid tertiary butyl ester, the first charging fire retardant and the second charging fire retardant are clorafin, thermo-stabilizer is a mercaptan trioctylphosphine tin, and all the other raw materials are all identical with embodiment 1.The rosin products that obtains is measured according to method identical among the embodiment 1, and the result is as shown in table 2.
Determination data from table 2 can be seen, owing to used the relatively low chlorinated polyethylene rubber of molecular weight, increased the usage quantity of chain-transfer agent simultaneously, though chlorinated polyethylene rubber and butadiene type rubber content do not descend too much, the breach resistance to impact shock of rosin products still has decline by a relatively large margin.Used the moderate clorafin of cl content as fire retardant among this embodiment, the fire retardant that therefore need add more amount just can reach the flame retardant rating of V-0, and the interpolation of a large amount of fire retardants affects greatly on physical and mechanical property rosin products.
The comparative example 8:
Compare with embodiment 1.According to the step among the embodiment 1, add with embodiment 1 in identical various raw materials, wherein second charging stock tank does not use the second charging fire retardant.Carry out the successive polymerization reaction according to the condition in the table 3, the rosin products that obtains is measured according to method identical among the embodiment 1, and the result is as shown in table 4.
Determination data from table 4 can see apparent in viewly, under the moderate situation of the first charging fire retardant usage quantity, do not adopt the second charging fire retardant after, the flame retardant properties of rosin products more significantly descends.
The comparative example 9:
Compare with embodiment 2.According to the step among the embodiment 2, add with embodiment 2 in identical various raw materials, wherein do not add butadiene type rubber among the comparative example 9.The rosin products that obtains is measured according to method identical among the embodiment 1, and the result is as shown in table 4.
Determination data from table 4 can be seen, after not using divinyl rubber, the breach resistance to impact shock of rosin products declines by a big margin, and rosin products promotes on antistatic property and weathering resistance and not obvious, illustrate add behind the butadiene type rubber small to the antistatic property and the weathering resistance influence of rosin products, and very big to the influence of breach resistance to impact shock, the chlorinated polyethylene rubber type of using among the embodiment has certain limitation to the raising of rosin products breach shock resistance.
The comparative example 10:
Compare with embodiment 3.According to the step among the embodiment 3, add with embodiment 3 in identical various raw materials, wherein do not add the first charging fire retardant and the second charging fire retardant among the comparative example 10.The rosin products that obtains is measured according to method identical among the embodiment 1, and the result is as shown in table 4.
Determination data from table 4 can be seen, owing to do not add fire retardant, though breach resistance to impact shock, physical and mechanical property, antistatic property and the weathering resistance of rosin products meet the demands, but rosin products does not reach the flame retardant rating of requirement, so rosin products will reach the flame retardant rating of V-0, the interpolation of fire retardant is essential.
Comparative example 11 and 12:
Compare with embodiment 5.According to the step among the embodiment 5, add with embodiment 5 in identical various raw materials, wherein the usage quantity of chlorinated polyethylene rubber increases to 12% and 16% respectively among the comparative example 11 and 12.The rosin products that obtains is measured according to method identical among the embodiment 1, and the result is as shown in table 4.
Determination data from table 4 can be seen, the breach resistance to impact shock of rosin products does not significantly increase along with the increase of chlorinated polyethylene rubber and butadiene type rubber content always, when rubber content reaches certain content, the raising of the breach resistance to impact shock of rosin products is limited, and when surpassing certain content, can descend to some extent on the contrary, this is because rubber content when too much, the level of graft polymerization that takes place descends on the contrary, and because rubber content is when too much, the dispersion of rubber particles and distribute has undesirablely caused the breach resistance to impact shock of rosin products to improve limited.
The comparative example 13:
Compare with embodiment 6.According to the step among the embodiment 6, add with embodiment 6 in identical various raw materials, wherein the chlorinated polyethylene rubber of interpolation is extra large brilliant CPE135 among the comparative example 13.The rosin products that obtains is measured according to method identical among the embodiment 1, and the result is as shown in table 4.
Determination data from table 4 can see, owing to used the relatively low chlorinated polyethylene rubber of chlorine weight percentage among the comparative example 13, the relative embodiment of the flame retardant properties of rosin products 6 is relatively poor, and other performances are suitable.
Table 4
| The comparative example | ??8 | ??9 | ??10 | ??11 | ??12 | ??13 | |
| Socle girder breach resistance to impact shock | ??kJ/m 2 | ??22.7 | ??15.7 | ??27.1 | ??39.5 | ??38.2 | ??29.1 |
| Tensile break strength | ??Mpa | ??37.2 | ??35.5 | ??39.8 | ??45.2 | ??43.5 | ??43.8 |
| Elongation at break | ??％ | ??34.3 | ??34.8 | ??38.4 | ??41.0 | ??39.4 | ??42.3 |
| The vertical combustion grade | Level | ??V-1 | ??V-0 | Not fire-retardant | ??V-0 | ??V-0 | ??V-1 |
| Volume specific resistance/10 12 | ??Ω·cm | ??1.4 | ??1.3 | ??1.5 | ??1.7 | ??1.56 | ??1.5 |
| 1000h artificial weathering socle girder breach shock resistance conservation rate | ??％ | ??74.9 | ??75.4 | ??74.2 | ??73.8 | ??74.9 | ??74.6 |
Table 3
Claims (10)
1. the method for preparing continuous bulk of flame retardant and highly impact resistant acrylonitrile-chlorinatedpolyethylene-styrene resin is characterized in that: comprise the steps:
1.1 rubber is dissolved in the mixing solutions of monoalkyl vinyl aromatic monomer, unsaturated nitrile monomer and solvent, mix the back with fire retardant, initiator, chain-transfer agent, oxidation inhibitor and form rubber solutions, enter first reactor as first charging and carry out graft polymerization reaction; Wherein, described rubber is the combination of chlorinated polyethylene rubber and butadiene type rubber, chlorinated polyethylene rubber weight average particle diameter 0.3-0.8 micron, butadiene type rubber weight average particle diameter 1.0-5.0 micron, the chlorinated polyethylene rubber molecular weight is 100,000-250,000, the butadiene type molecular weight rubber is 150,000-350,000, chlorinated polyethylene rubber chlorine weight percentage is 20-45%, the butadiene type rubber weight percentage that adds is 1-5%, and the fire retardant weight percentage of interpolation is 0-8%;
1.2 with the polymerisate of first charging in first reactor in the described step 1.1 and the second charging thorough mixing that contains the aromatic hydrocarbon mixing solutions of fire retardant, enter second reactor, proceed graft polymerization reaction and particle-stabilised, rubber weight average particle diameter 0.3-1.2 micron;
The add-on of the described second charging fire retardant is the 2-10% of the first charging rubber solutions weight;
1.3 with the polymerisate of first charging in first reactor in the described step 1.1 and the additive charging thorough mixing that contains the aromatic hydrocarbon mixing solutions of thermo-stabilizer, lubricant, enter second reactor, proceed graft polymerization reaction and particle-stabilised;
1.4 the material that will discharge from second reactor separates through the secondary devolatilization, extruding pelletization obtains flame retardant and highly impact resistant acrylonitrile-chlorinatedpolyethylene-styrene resin, rubber weight average particle diameter 0.3-1.0 micron wherein, and rubber content is 15-30%.
2. the method for preparing continuous bulk of flame retardant and highly impact resistant acrylonitrile-chlorinatedpolyethylene as claimed in claim 1-styrene resin is characterized in that:
In the described step 1.1: first charging polyreaction solids content to the polymerisate in first reactor is 35-55%, first feed rate is 800-1500ml/h, temperature of reaction 100-125 ℃, reaction pressure 0.3-1.0MPa, stirring velocity 40-160 rev/min;
In described step 1.2, the step 1.3: first charging polyreaction solids content to the polymerisate in second reactor is 55-80%, temperature of reaction 125-155 ℃, and reaction pressure 0.3-1.0MPa, stirring velocity 20-70 rev/min;
In described step 1.2, the step 1.3: the feed rate of second charging and additive charging is 50-200ml/h, stirring velocity 30-100 rev/min.
In the described step 1.4: adopt the secondary devolatilization system, one-level devolatilizer pressure is normal pressure or pressure-fired, and secondary devolatilizer pressure is negative pressure, and the devolatilizer temperature is 160-220 ℃.
3. as the method for preparing continuous bulk of right 2 described flame retardant and highly impact resistant acrylonitrile-chlorinatedpolyethylene-styrene resins, it is characterized in that:
In the described step 1.4, adopt the two-stage devolatilization extrusion step of differing temps and pressure, one-level devolatilizer absolute pressure is 101-120kpa, and one-level devolatilizer temperature is 160-180 ℃, and secondary devolatilizer absolute pressure is 1-20kpa, and secondary devolatilizer temperature is 200-220 ℃;
In the described step 1.4, in the secondary devolatilization process, adopt to remove agent.
4. as the method for preparing continuous bulk of claim 1 or 2 or 3 described flame retardant and highly impact resistant acrylonitrile-chlorinatedpolyethylene-styrene resins, it is characterized in that:
In the first charging rubber solutions gross weight is 100%, and monoalkyl vinyl aromatic monomer content is 37-53%, and unsaturated nitrile monomer content is 12-18%, and chlorinated polyethylene rubber content is 8-16%, and the first charging flame retardant agent content is 0-8%;
Described butadiene type rubber weight is the 1-5% of the first charging rubber solutions weight;
Described weight of solvent is the 10-30% of the first charging rubber solutions weight;
Described initiator weight is the 0.03-0.2% of the first charging rubber solutions weight;
Described chain-transfer agent weight is the 0.2-0.8% of the first charging rubber solutions weight;
Described oxidation inhibitor weight is 0.2-0.6%;
Described thermo-stabilizer weight is the 0.2-1.5% of the first charging rubber solutions weight;
Described lubricant weight is the 0.3-1.6% of the first charging rubber solutions weight.
5. as the method for preparing continuous bulk of claim 1 or 2 or 3 described flame retardant and highly impact resistant acrylonitrile-chlorinatedpolyethylene-styrene resins, it is characterized in that:
Described chlorinated polyethylene rubber is resin type chlorinated polyethylene rubber and/or rubber-type chlorinated polyethylene rubber, rubber is 80 by molecular weight, 000-230,000 polyethylene direct chlorination obtains, molecular weight rubber is 100,000-250,000, the rubber weight average particle diameter is the 0.3-0.6 micron, and rubber chlorine weight percentage is 30-45%;
Described butadiene type rubber is one or more in the following substances: low-cis-polybutadiene rubber, cis-rich polybutadiene rubber and butadiene-styrene block copolymer, molecular weight rubber is 200,000-300,000, rubber weight average particle diameter 1.2-4.0 micron;
Described monoalkyl vinyl aromatic monomer is one or more in the following substances: vinylbenzene, alpha-methyl styrene, α-ethyl styrene, neighbour-,-and p-methylstyrene, 2,4-dimethyl styrene, right-t-butyl styrene, α-ethyl p-methylstyrene, neighbour-,-and right-chloro-styrene, neighbour-bromstyrol, 2,4-Dowspray 9,2-methyl-4-chloro-styrene, 2,6-two chloro-4-vinyl toluenes;
Described unsaturated nitrile monomer is one or more of following substances: vinyl cyanide, Alpha-Methyl vinyl cyanide, ethyl acrylonitrile;
Described solvent is aliphatic ketone and/or aromatic hydrocarbon, and wherein, described aliphatic ketone is one or more in acetone, methyl ethyl ketone, the methyl propyl ketone, and described aromatic hydrocarbon is one or more in benzene, toluene, the ethylbenzene.
6. the method for preparing continuous bulk of flame retardant and highly impact resistant acrylonitrile-chlorinatedpolyethylene as claimed in claim 4-styrene resin is characterized in that:
Described chlorinated polyethylene rubber is resin type chlorinated polyethylene rubber and/or rubber-type chlorinated polyethylene rubber, rubber is 80 by molecular weight, 000-230,000 polyethylene direct chlorination obtains, molecular weight rubber is 100,000-250,000, the rubber weight average particle diameter is the 0.3-0.6 micron, and rubber chlorine weight percentage is 30-45%;
Described butadiene type rubber is one or more in the following substances: low-cis-polybutadiene rubber, cis-rich polybutadiene rubber and butadiene-styrene block copolymer, molecular weight rubber is 200,000-300,000, rubber weight average particle diameter 1.2-4.0 micron;
Described monoalkyl vinyl aromatic monomer is one or more in the following substances: vinylbenzene, alpha-methyl styrene, α-ethyl styrene, neighbour-,-and p-methylstyrene, 2,4-dimethyl styrene, right-t-butyl styrene, α-ethyl p-methylstyrene, neighbour-,-and right-chloro-styrene, neighbour-bromstyrol, 2,4-Dowspray 9,2-methyl-4-chloro-styrene, 2,6-two chloro-4-vinyl toluenes;
Described unsaturated nitrile monomer is one or more of following substances: vinyl cyanide, Alpha-Methyl vinyl cyanide, ethyl acrylonitrile;
Described solvent is aliphatic ketone and/or aromatic hydrocarbon, and wherein, described aliphatic ketone is one or more in acetone, methyl ethyl ketone, the methyl propyl ketone, and described aromatic hydrocarbon is one or more in benzene, toluene, the ethylbenzene.
7. as the method for preparing continuous bulk of claim 1 or 2 or 3 described flame retardant and highly impact resistant acrylonitrile-chlorinatedpolyethylene-styrene resins, it is characterized in that:
Described initiator is one or more of following substances: t-butyl perbenzoate, sec.-propyl percarbonic acid tertiary butyl ester, cross sad tertiary butyl ester, cross different n-nonanoic acid tertiary butyl ester, 2-ethylhexyl list peroxide carbonic acid tertiary butyl ester, cross the neodecanoic acid tertiary butyl ester;
Described chain-transfer agent is preferably one or more in linear dimer, n-butyl mercaptan, tert-butyl mercaptan, octyl mercaptan, the lauryl mercaptan;
Described fire retardant is one or more of following substances: tetrabromo-bisphenol diphenyl phosphoester, Resorcinol two phenyl phosphate ester (RDP), tetrabromo-phthalate glycol, tricresyl phosphate (2-chloroethyl) ester, triaryl phosphate, cyclisation phosphoric acid ester, clorafins, close halogen polyether glycol, tetrabromo-bisphenol, tetrabromo-bisphenol epoxy oligomer, brominated Polystyrene, 1,2-two (2,4,6-tribromophenoxy) ethane, the two tetrabromo phthalimides of ethylene, decabrominated dipheny base ethane, decabromodiphenyl oxide, antimony tetroxide, antimonous oxide, tellurium dioxide;
Described thermo-stabilizer is one or more in the following substances: dibutyl tin laurate, toxilic acid dibutyl tin, lauric acid toxilic acid dibutyl tin, thiol methyl tin, mercaptan trioctylphosphine tin, barium/cadmium carboxylate stabilizer, barium/zinc composite stabilizer, calcium/zinc composite stabilizer, calcium stearate, Zinic stearas, lead sulfate tribasic, second base lead sulfate;
Described lubricant is one or more in the following substances: paraffin, polyethylene wax, Zerol, stearyl alcohol, pentaerythritol ester, stearic amide, erucicamide, ethylene bis stearamide.
8. the method for preparing continuous bulk of flame retardant and highly impact resistant acrylonitrile-chlorinatedpolyethylene as claimed in claim 4-styrene resin is characterized in that:
Described initiator is one or more of following substances: t-butyl perbenzoate, sec.-propyl percarbonic acid tertiary butyl ester, cross sad tertiary butyl ester, cross different n-nonanoic acid tertiary butyl ester, 2-ethylhexyl list peroxide carbonic acid tertiary butyl ester, cross the neodecanoic acid tertiary butyl ester;
Described chain-transfer agent is preferably one or more in linear dimer, n-butyl mercaptan, tert-butyl mercaptan, octyl mercaptan, the lauryl mercaptan;
Described fire retardant is one or more of following substances: tetrabromo-bisphenol diphenyl phosphoester, Resorcinol two phenyl phosphate ester (RDP), tetrabromo-phthalate glycol, tricresyl phosphate (2-chloroethyl) ester, triaryl phosphate, cyclisation phosphoric acid ester, clorafins, close halogen polyether glycol, tetrabromo-bisphenol, tetrabromo-bisphenol epoxy oligomer, brominated Polystyrene, 1,2-two (2,4,6-tribromophenoxy) ethane, the two tetrabromo phthalimides of ethylene, decabrominated dipheny base ethane, decabromodiphenyl oxide, antimony tetroxide, antimonous oxide, tellurium dioxide;
Described thermo-stabilizer is one or more in the following substances: dibutyl tin laurate, toxilic acid dibutyl tin, lauric acid toxilic acid dibutyl tin, thiol methyl tin, mercaptan trioctylphosphine tin, barium/cadmium carboxylate stabilizer, barium/zinc composite stabilizer, calcium/zinc composite stabilizer, calcium stearate, Zinic stearas, lead sulfate tribasic, second base lead sulfate;
Described lubricant is one or more in the following substances: paraffin, polyethylene wax, Zerol, stearyl alcohol, pentaerythritol ester, stearic amide, erucicamide, ethylene bis stearamide.
9. the method for preparing continuous bulk of flame retardant and highly impact resistant acrylonitrile-chlorinatedpolyethylene as claimed in claim 5-styrene resin is characterized in that:
Described initiator is one or more of following substances: t-butyl perbenzoate, sec.-propyl percarbonic acid tertiary butyl ester, cross sad tertiary butyl ester, cross different n-nonanoic acid tertiary butyl ester, 2-ethylhexyl list peroxide carbonic acid tertiary butyl ester, cross the neodecanoic acid tertiary butyl ester;
Described chain-transfer agent is preferably one or more in linear dimer, n-butyl mercaptan, tert-butyl mercaptan, octyl mercaptan, the lauryl mercaptan;
Described fire retardant is one or more of following substances: tetrabromo-bisphenol diphenyl phosphoester, Resorcinol two phenyl phosphate ester (RDP), tetrabromo-phthalate glycol, tricresyl phosphate (2-chloroethyl) ester, triaryl phosphate, cyclisation phosphoric acid ester, clorafins, close halogen polyether glycol, tetrabromo-bisphenol, tetrabromo-bisphenol epoxy oligomer, brominated Polystyrene, 1,2-two (2,4,6-tribromophenoxy) ethane, the two tetrabromo phthalimides of ethylene, decabrominated dipheny base ethane, decabromodiphenyl oxide, antimony tetroxide, antimonous oxide, tellurium dioxide;
Described thermo-stabilizer is one or more in the following substances: dibutyl tin laurate, toxilic acid dibutyl tin, lauric acid toxilic acid dibutyl tin, thiol methyl tin, mercaptan trioctylphosphine tin, barium/cadmium carboxylate stabilizer, barium/zinc composite stabilizer, calcium/zinc composite stabilizer, calcium stearate, Zinic stearas, lead sulfate tribasic, second base lead sulfate;
Described lubricant is one or more in the following substances: paraffin, polyethylene wax, Zerol, stearyl alcohol, pentaerythritol ester, stearic amide, erucicamide, ethylene bis stearamide.
10. the method for preparing continuous bulk of flame retardant and highly impact resistant acrylonitrile-chlorinatedpolyethylene as claimed in claim 6-styrene resin is characterized in that:
Described initiator is one or more of following substances: t-butyl perbenzoate, sec.-propyl percarbonic acid tertiary butyl ester, cross sad tertiary butyl ester, cross different n-nonanoic acid tertiary butyl ester, 2-ethylhexyl list peroxide carbonic acid tertiary butyl ester, cross the neodecanoic acid tertiary butyl ester;
Described chain-transfer agent is preferably one or more in linear dimer, n-butyl mercaptan, tert-butyl mercaptan, octyl mercaptan, the lauryl mercaptan;
Described fire retardant is one or more of following substances: tetrabromo-bisphenol diphenyl phosphoester, Resorcinol two phenyl phosphate ester (RDP), tetrabromo-phthalate glycol, tricresyl phosphate (2-chloroethyl) ester, triaryl phosphate, cyclisation phosphoric acid ester, clorafins, close halogen polyether glycol, tetrabromo-bisphenol, tetrabromo-bisphenol epoxy oligomer, brominated Polystyrene, 1,2-two (2,4,6-tribromophenoxy) ethane, the two tetrabromo phthalimides of ethylene, decabrominated dipheny base ethane, decabromodiphenyl oxide, antimony tetroxide, antimonous oxide, tellurium dioxide;
Described thermo-stabilizer is one or more in the following substances: dibutyl tin laurate, toxilic acid dibutyl tin, lauric acid toxilic acid dibutyl tin, thiol methyl tin, mercaptan trioctylphosphine tin, barium/cadmium carboxylate stabilizer, barium/zinc composite stabilizer, calcium/zinc composite stabilizer, calcium stearate, Zinic stearas, lead sulfate tribasic, second base lead sulfate;
Described lubricant is one or more in the following substances: paraffin, polyethylene wax, Zerol, stearyl alcohol, pentaerythritol ester, stearic amide, erucicamide, ethylene bis stearamide.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102690396A (en) * | 2012-05-30 | 2012-09-26 | 宁波镇洋化工发展有限公司 | Polymerization method for continuous body of acrylate, chlorinated polyethylene rubber and styrol resin |
| CN104558429A (en) * | 2013-10-18 | 2015-04-29 | 中国石油化工股份有限公司 | Production method of polystyrene composition and polystyrene composition obtained by using production method |
| CN102514305B (en) * | 2002-10-10 | 2016-03-16 | 霍尼韦尔国际公司 | Shock-resistant and fire-resistant composite article |
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| US3496251A (en) * | 1964-01-24 | 1970-02-17 | Showa Denko Kk | Chlorinated polyethylene graft copolymer and blends containing same |
| CN1240623C (en) * | 2004-09-08 | 2006-02-08 | 东莞理工学院 | Integrated waste water treating method by flocculation, adsorption, oxidation degradation and filtering |
| CN100402603C (en) * | 2006-08-15 | 2008-07-16 | 杭州科利化工有限公司 | Preparation method for flame-proof acrylonitrile-styrene copolymerized resin/acrylonitrile-chlorided polyethylene-styrene copolymerized resinplastic alloy |
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| CN102514305B (en) * | 2002-10-10 | 2016-03-16 | 霍尼韦尔国际公司 | Shock-resistant and fire-resistant composite article |
| CN102690396A (en) * | 2012-05-30 | 2012-09-26 | 宁波镇洋化工发展有限公司 | Polymerization method for continuous body of acrylate, chlorinated polyethylene rubber and styrol resin |
| CN102690396B (en) * | 2012-05-30 | 2014-04-23 | 宁波镇洋化工发展有限公司 | Polymerization method for continuous body of acrylate, chlorinated polyethylene rubber and styrol resin |
| CN104558429A (en) * | 2013-10-18 | 2015-04-29 | 中国石油化工股份有限公司 | Production method of polystyrene composition and polystyrene composition obtained by using production method |
| CN106188910A (en) * | 2016-07-08 | 2016-12-07 | 广安奥海通讯电子科技有限公司 | A kind of mobile phone shell material and preparation method thereof |
| CN108299601A (en) * | 2017-12-12 | 2018-07-20 | 北方华锦化学工业股份有限公司 | A kind of continuous bulk prepares high flowing, high-impact ABS resin |
| CN111748170A (en) * | 2020-07-16 | 2020-10-09 | 雷丽 | Modified ABS resin and production process thereof |
| CN112094681A (en) * | 2020-08-20 | 2020-12-18 | 安徽绿环泵业有限公司 | Preparation method of lubricating sealing filler for corrosion-resistant pump |
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