CN102492064B - Preparation and application method of polyvinyl chloride (PVC) resin terminator - Google Patents
Preparation and application method of polyvinyl chloride (PVC) resin terminator Download PDFInfo
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- CN102492064B CN102492064B CN201110380532.9A CN201110380532A CN102492064B CN 102492064 B CN102492064 B CN 102492064B CN 201110380532 A CN201110380532 A CN 201110380532A CN 102492064 B CN102492064 B CN 102492064B
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Abstract
The invention relates to a preparation and application method of a polyvinyl chloride (PVC) resin terminator, belonging to the technical field of chemical products. The invention particularly relates to a liquid antioxidant product, which mainly comprises 2,6-di-bert-butyl-4-(1-phenylethyl)phenol and is obtained by carrying out catalytic alkylation reaction on 2,6-di-bert-butyl phenol and styrene as raw materials. An organic solvent is added into the liquid antioxidant product which mainly comprises the 2,6-di-bert-butyl-4-(1-phenylethyl)phenol, and is sufficiently stirred to obtain the liquid antioxidant product HKY-10. The HKY-10 is compounded with a benzofuran ketone antioxidant and a phosphite ester antioxidant to obtain an oil-soluble compound liquid terminator product as a terminator for a general-purpose PVC resin product preparation process by a suspension method; and the liquid terminator is added in a polymerization reaction process to obtain a PVC resin product with stable properties, thereby enhancing the aging whiteness of the PVC resin product. The PVC resin terminator has the characteristics of no toxicity and environmental protection, and does not generate water pollutants.
Description
Technical field
The present invention is a kind of preparation method of polyvinyl chloride resin terminator, for improving the method for the universal polyvinyl chloride of suspension method (PVC) rosin products stability.Being specifically related to by 2,6 di t butyl phenol, vinylbenzene is raw material, catalytic alkylation reaction preparation formula (
) be the liquid antioxidant product of principal product, both 2,6-di-t-butyl-4-(1-phenylethyl) the phenol liquid antioxidant product that is principal product; Relate to technical field of chemical products;
（
）
At 2,6-di-t-butyl-4-(1-phenylethyl) add organic solvent in the phenol liquid antioxidant product that is principal product, fully stir, make liquid antioxidant product HKY-10.
Background technology
Be raw material by 2,6 di t butyl phenol, vinylbenzene, catalytic alkylation reaction preparation formula (
) add organic solvent in the liquid antioxidant product of principal product, fully stir, make liquid antioxidant product HKY-10, a kind of benzofuranone kind antioxidant and a kind of phosphite ester kind antioxidant are compound, make a kind of oil soluble, compound, liquid terminator product, prepare the terminator in universal polyvinyl chloride resin Product Process process as suspension method, in polymerization process, add, to obtain the polyvinyl chloride resin product with stability, improve ageing whiteness.Aqueous suspension polymerization is the main method of synthetic polyvinyl chloride resin, in water solution system, add dispersion agent, buffer reagent, initiator, auxiliary agent and the vinyl chloride monomer reaction raw materials such as pH value conditioning agent, under the effect of stirring, make reactant high dispersing and become stable emulsion, protective colloid in water is dispersed in vinyl chloride monomer in small drop, each drop is equivalent to a polymerization system, the initiator that is dissolved in monomer resolves into free radical under polymerization temperature, cause the polymerization of vinyl chloride monomer, whole polymerization process comprises that chain causes, chainpropagation, the unit processes such as chain termination, the polyvinyl chloride generating is insoluble in monomer phase vinylchlorid, initial reaction stage is just precipitated out mutually from vinyl chloride monomer, the solidifying primary particle of wadding a quilt with cotton into, and finally grow into primary particle, primary particle clinkering and assembling, formation has internal pore structure PVC particle, both polyvinyl chloride resin product.
It is the reaction that monomer forms free radical activity center that chain causes, generally include decomposition of initiator and form elementary free radical R,
Elementary free radical and VCM addition, form monomer free radical CH
2two steps of CHCI; The chainpropagation stage is to cause on the basis that forms monomer free radical at chain, and constantly addition monomer molecule makes chainpropagation form macromole; Termination step comprises that free radical interacts and stops, and the living chain free radical of two growths interacts and makes chain termination, and therefore the termination reaction of radical polymerization is dimolecular reaction, has two kinds of forms of coupling and disproportionation.Polymerization process later stage monomer concentration is lower, if dependence reaction stops automatically, stops occupying an leading position with double-basis disproportionation, and two large PVC free radical molecules meet a saturated macromole of formation and stop; Another is the unsaturated termination with two keys, and result causes generated small molecules quality PVC, with the PVC of side chain, increase with the PVC product of chlorallylene structure.There is the PVC thermostability extreme difference of this molecular structure, especially on molecular chain, there is chlorallylene, there is height activity, in the situation of being heated, be easy to dehydrochlorination, form conjugated polyene structure, the HCl that deviates from of starting stage becomes again PVC macromolecular chain continues the catalyzer of thermolysis, therefore, the reaction of dehydrochlorination Once you begin, will make further reaction become more easy, cause polyvinyl chloride resin product generation thermal ageing, yellow exponent increase whiteness reduces.In addition under the effect of heat or light, there is the homolysis of C-Cl key and generate high molecular free radical R, due to the reaction activity of free radical, can carry out intermolecular or intramolecular further reaction stable to obtain, in the situation that aerobic exists, be easy to occur the oxidizing reaction of free radical especially, generate oxyradical RO, peroxylradicals ROO, thereby further promote the molecule crosslinked of polyvinyl chloride, both caused the aging generation of polyvinyl chloride.For this reason, must in the time that arriving the terminal of setting, polyreaction start to add terminator, during polyreaction terminal is approximately chosen in transformation efficiency 70 ~ 85%, in order to improve the stability of PVC product, need to eliminate the free radical and the residual initiators that remain in resin, also be the important evidence of design terminator compositing formula, good terminator can be rapidly remaining initiator in still, elementary free radical, monomer free radical, the living chain radical termination increasing, inactivation, less desirable reflex action is stopped immediately, to obtain the good stability PVC molecular structure that has.Through polyvinyl chloride pulp centrifuged filtration, in terminator, the oxidation inhibitor of various effects is dispersed in the PVC product of porous particle, continue that performance is caught initiator activity group, caught oxyradical, the effect of peroxylradicals, hydroperoxide decomposition, make polyvinyl chloride resin product in follow-up production technique and storage, use procedure in there is higher thermostability.
Terminator product needed is made liquid dosage form, solution dosage or water miscible liquid formulation and just can be convenient to be dispersed in the PVC product of porous particle, the effectively function of performance terminator, if the form with pressed powder adds, form solid-liquid nonhomogeneous system, it is very low stopping usefulness.
The terminator that open report is produced PVC has BHT, dihydroxyphenyl propane, antioxidant 1010, 1076, 2246, 168 etc., phenolic antioxidant can make its inactivation with free radical reaction, there is obvious effect for eliminating the thermolability of bringing due to oxygen, to resin thermo oxidative aging, improve ageing whiteness and also have certain effect, but phenolic antioxidant can not with initiator for reaction, the initiator that remains in resin particle inside still can cause the accelerated deterioration of PVC product in follow-up operation, conventionally under one-component service condition, efficiency is very low, general large usage quantity, in addition, use BHT, dihydroxyphenyl propane, 1010, 1076, 2246, in 168 processes, be dissolved into liquid dosage form by relatively large alcohol organic solvent, final alcohol organic solvent enters in polyvinyl chloride pulp centrifuged mother liquor, the COD of its waste discharge is obviously increased.Dihydroxyphenyl propane is the phenols that toxicity is stronger, has certain solubility in water, and in use procedure, a part remains in mother liquor and polluted water environment.
Acetone semicarbazone thiocarbamide (ATSC) is a kind of terminator of excellent property, can be fast and free radical and initiator for reaction, for eliminating polymerization later stage small molecules and branched chain molecule, and then the thermostability that improves product has certain effect, but not obvious to the effect of resin thermo oxidative aging.
The toxicity of dihydroxyphenyl propane, ATSC product and the negative impact that brings for PVC terminator are for people's common recognition, because toxic effect has been limited use.
Chinese patent CN101735357A discloses a kind of method that improves ageing whiteness of vinyl chloride resin, wherein take acetone semicarbazone thiocarbamide as terminator, the aqueous emulsion type oxidation inhibitor EB44-34 that makes as anti-flake agent, Ciba company half hindered phenol antioxygen of Tert. Butyl Hydroquinone is chain terminator, its weak point is the ATSC material that has used toxicity larger.
Chinese patent CN101921354A discloses the preparation method of the high polyvinyl chloride (PVC) RESINS of a kind of transparency, wherein take acetone semicarbazone thiocarbamide or diethyl hydroxylamine as single terminator, or composite with the one in sulfo-propanedioic acid two lauryls and BHT, dihydroxyphenyl propane, antioxidant 1076,1010, as terminator, its weak point is the ATSC material that has used toxicity larger; Or the BHT, the dihydroxyphenyl propane product that ecotope are had to negative effect are used.
Chinese patent CN1657546A discloses the universal polyvinyl chloride (PVC) RESINS preparation method of a kind of suspension method, wherein, take acetone semicarbazone thiocarbamide as single terminator, is mixed with 3 ~ 10% the aqueous solution when use, and its weak point is the ATSC material that has used toxicity larger.
Chinese patent CN1654486A discloses the multiplexing method of centrifugal slurry mother liquor in a kind of polyvinyl chloride (PVC) RESINS preparation process, wherein take acetone semicarbazone thiocarbamide or antioxidant as single terminator.
Chinese patent CN1649913A discloses a kind of chain termination method of PVC polymerization, is wherein complex as terminator with dissociate nitroxyl and phenolic antioxidant,
In the method for the disclosed vinylchlorid aqueous suspension polymerization of Chinese patent CN1501945A, used nitroxide type stable free radical as polymerization terminator, or the mixture of nitroxide type stable free radical material and diethyl hydroxylamine is terminator.
Terminator of the present invention is a kind of oil soluble, compound, liquid product, prepare the terminator in universal polyvinyl chloride resin Product Process process as suspension method, in polymerization process, set terminal time add, make residue initiator in still, elementary free radical, monomer free radical, the living chain free radical Quick stop increasing, inactivation, avoid containing in the finished product small molecules quality PVC, with the PVC of side chain, with the PVC of chlorallylene structure, to obtain the polyvinyl chloride resin product with stability, from angle analysis intuitively, evaluate: the polyvinyl chloride resin product of acquisition has high whiteness and ageing whiteness.
Summary of the invention
The present invention is for overcoming above-mentioned deficiency of the prior art, a kind of oil soluble, compound, liquid terminator product are invented, prepare the terminator in universal polyvinyl chloride resin Product Process process as suspension method, in polymerization process, select vinyl chloride monomer transformation efficiency to add during 70 ~ 90%, to obtain the polyvinyl chloride resin product with stability.
The HKY-10 that the compound liquid terminator of oil soluble product is prepared by the present invention forms with a kind of benzofuranone kind antioxidant and a kind of phosphite ester kind antioxidant.
The preparation method of a kind of polyvinyl chloride resin terminator of the present invention, carries out according to following step:
(1) prepare HKY-10: for raw material, vinylbenzene is alkylating reagent with 2,6 di t butyl phenol (being called for short 2,6-phenol); Employing organic acid compound is catalyzer, add a small amount of stopper, carry out catalytic alkylation reaction generation with 2,6-di-t-butyl-4-(1-phenylethyl) the phenol liquid mixture that is principal product, after reaction finishes, cooling, in adding and discoloring agent, organic solvent, fully stir, make the phenylethyl with 2,6-di-t-butyl-4-(1-) phenol be principal product liquid antioxidant product, i.e. HKY-10;
(2) HKY-10 is added in reactor in proportion successively with a kind of benzofuranone kind antioxidant and a kind of phosphite ester kind antioxidant, stir, be warming up to 50 ~ 80 ℃, fully stir 30 ~ 60 minutes, make the compound liquid terminator of oil soluble product.
Organic acid catalyst described in step (1) refers to: Witco 1298 Soft Acid, hexadecyl Phenylsulfonic acid, octadecyl Phenylsulfonic acid, two Witco 1298 Soft Acid, double hexadecyl Phenylsulfonic acid, two octadecyl Phenylsulfonic acid, decyl phenyl ether disulfonic acid, dodecyl diphenyl oxide disulfonic acid, hexadecyl phenyl ether disulfonic acid, two dodecyl diphenyl oxide disulfonic acid, double hexadecyl phenyl ether disulfonic acid, preferably Witco 1298 Soft Acid.
Stopper described in step (1) refers to: 2,6-di-t-butyl-4-methylphenol; 2,2 '-ethylene two (4,6-di-tert-pentyl phenol); 2,2 '-ethylene two (4,6-DI-tert-butylphenol compounds); 2,2 '-methylene-bis (4,6-di-tert-pentyl phenol); 2,2 '-methylene-bis (4,6-DI-tert-butylphenol compounds); 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol); 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol).β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) the positive octadecyl ester of propionic acid, four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, phosphorous acid (three nonyl phenyl) ester, diphosphorous acid pentaerythritol stearic acid ester 2, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (different tridecanol base) pentaerythritol diphosphites.
In described in step (1), refer to discoloring agent: aminated compounds and Na
2cO
310H
2the mixture of O.Aminated compounds refers to: diethylamine; Triethylamine; Dipropyl amine; Tripropyl amine; Trioctylamine; Quadrol; 1,2-propylene diamine; N-hydroxyethyl-ethylenediamine; N, N-dimethylethanolamine; N, N-diethylethanolamine; Dimethyl hydroxylamine; Diethyl hydroxylamine; N-isopropylhydroxyla; Diethanolamine; Trolamine; Diisopropanolamine (DIPA); One in tri-isopropanolamine.
Organic solvent described in step (1) refers to: vinylbenzene; α-vinyl toluene; C
10~ C
16straight-chain paraffin or isoparaffin.
Proportioning raw materials processed described in step (1) is 2,6-phenol: vinylbenzene (mol ratio) is 1:0.60 ~ 2.0; Preferably suitable proportioning raw materials is 1:0.80 ~ 1.2.
Described in step (1), the addition of catalyzer shows the phenol with 2,6-: catalyzer (mass ratio) is 1:0.02 ~ 0.2, and preferably suitable mass ratio is 1:0.07 ~ 0.1.
The addition of the stopper described in step (1) shows the phenol with 2,6-: stopper (mass ratio) is 1:0.001-0.020; Selecting suitable mass ratio is 1:0.002-0.008.
Temperature of reaction described in step (1) is 80-120 ℃; Under temperature of reaction, employing vinylbenzene drips continuously feeding manner and 2,6-phenol reacts, and it is 180 ~ 240 minutes that suitable vinylbenzene drips feed time; After charging completes, under temperature of reaction, selecting the suitable insulation reaction time is 60 ~ 80 minutes.
The cooling that step (1) is described, selecting suitable cooling temperature is 60 ~ 80 ℃, in adding and discoloring agent, and maintains at this temperature and stirs 20 ~ 30 minutes.
In described in step (1) and discoloring agent add-on by the mass ratio meter of itself and 2,6-phenol, 2,6-phenol: aminated compounds (mass ratio)=1:0.01 ~ 0.10, suitable mass ratio is 1:0.05 ~ 0.10; In and discoloring agent in Na
2cO
310H
2o add-on is the molar ratio computing of Witco 1298 Soft Acid by itself and organic acid catalyst, selects Na
2cO
310H
2o: Witco 1298 Soft Acid (mol ratio)=1:2.
Organic solvent add-on described in step (1) is by itself and generation 2,6-di-t-butyl-4-(1-phenylethyl) the mass ratio meter of the phenol liquid mixture that is principal product, select suitable generation 2,6-di-t-butyl-4-(1-phenylethyl) the phenol liquid mixture that is principal product: organic solvent (mass ratio)=1:0.6 ~ 0.7.
Benzofuranone kind antioxidant described in step (2) refers to: 5,7-di-t-butyl-3-(4-methyl), 3 hydrogen-benzofuran-2-ones; 5,7-di-t-butyl-3-(3,4-dimethyl), 3 hydrogen-benzofuran-2-ones; 5,7-di-t-butyl-3-(2,4-dimethyl) 3 hydrogen-benzofuran-2-ones or; 5,7-di-t-butyl-3-(2,3-dimethyl), 3 hydrogen-benzofuran-2-ones;
Phosphite ester kind antioxidant described in step (2) refers to the phosphite ester compound with Spirocyclic structure, and structural formula is as follows:
The phosphite ester kind antioxidant of Spirocyclic structure
As: two (different tridecanol base) pentaerythritol diphosphites; Two (phenylcarbinol base) pentaerythritol diphosphites; Two (lauryl alcohol base) pentaerythritol diphosphites; Two (hexadecanol base) pentaerythritol diphosphites; Two (stearyl alcohol base) pentaerythritol diphosphites.
Making in the compound liquid terminator of oil soluble product process described in step (2), the mixing ratio of three kinds of oxidation inhibitor is measured take the organic solvent in HKY-10 as benchmark, wherein: the mass ratio of the organic solvent in HKY-10 and a kind of benzofuranone kind antioxidant is 1:0.001 ~ 0.3, suitable mass ratio is 1:0.08 ~ 0.10; Organic solvent in HKY-10 and a kind of mass ratio of phosphite ester kind antioxidant are: 1:0.01 ~ 1.2, suitable mass ratio is 1:0.2 ~ 0.5.
The using method of a kind of polyvinyl chloride resin of the present invention terminator, prepare in universal polyvinyl chloride resin Product Process process in known method, select vinyl chloride monomer transformation efficiency during 70 ~ 85%, to add terminator product of the present invention, add-on is pressed into 0. 05 ~ 0.08% of still vinyl chloride monomer massfraction.
advantage of the present invention
1, the present invention's selection is raw material by 2,6 di t butyl phenol, vinylbenzene, catalytic alkylation reaction preparation formula (
) shown in chemical structure, both 2,6-di-t-butyl-4-(1-phenylethyl) oxybenzene compound, after compound with benzofuranone kind antioxidant, phosphite ester kind antioxidant, very good with polyvinyl chloride resin consistency, in the PVC of porous particle product, be uniformly dispersed, even under 160 ~ 200 ℃ of state of temperatures, terminator is difficult for forming migration, volatilization loss.
2, the present invention, take HKY-10, benzofuranone kind antioxidant, phosphite ester kind antioxidant as raw material, makes a kind of oil soluble, compound, liquid terminator product, and this system has good synergistic effect, stops efficiency high, and consumption is little; Terminator is easily dispersed in polymerization liquid, easy to use.In polymerization process, set terminal time add, make residue initiator, elementary free radical, monomer free radical, the living chain free radical Quick stop of growth, inactivation in still, avoid containing in the finished product small molecules quality PVC, with the PVC of side chain, with the PVC of chlorallylene structure, to obtain the polyvinyl chloride resin product with stability, it has high whiteness and ageing whiteness.
3, the compound liquid terminator of oil soluble of the present invention has the advantages that production technique is simple, raw material is easy to get, product use cost is low, be convenient to industrial application.
4, the compound liquid terminator of oil soluble of the present invention has feature nontoxic, environmental protection, does not produce water pollutant.
Embodiment
Two (different tridecanol base) pentaerythritol diphosphites used in the present invention is product prepared by Changzhou University, and outward appearance is colourless liquid; Other raw material, as: 2,6 di t butyl phenol, vinylbenzene, α-vinyl toluene, organic acid catalyst, stopper, in and discoloring agent, benzofuranone kind antioxidant, phosphite ester kind antioxidant be commercially available prod, specification is industrial top grade product.
The using method of a kind of polyvinyl chloride resin of the present invention terminator, prepare in universal polyvinyl chloride resin Product Process process with known method, select vinyl chloride monomer transformation efficiency during 70 ~ 85%, to add compound liquid terminator product of the present invention, to obtain the polyvinyl chloride resin product with stability, improve ageing whiteness.
Consider better to understand content of the present invention from following non-limiting example 1 ~ 4.
One,
the preparation of the compound liquid terminator of oil soluble product
embodiment 1
In the 3000ml four-hole boiling flask that agitator, thermometer, vinylbenzene dropping funnel, reflux exchanger and nitrogen ingress pipe are housed, add 750 gram 2; 6-DI-tert-butylphenol compounds, 60 grams of Witco 1298 Soft Acids, the stopper of 2.5 grams; open and stir; pass into nitrogen and do nitrogen protection; slowly be warming up to 110 ~ 112 ℃, start to drip vinylbenzene at this temperature, vinylbenzene feeding quantity is 455 grams; at the uniform velocity drip and completed in 195 ~ 200 minutes, 110 ~ 112 ℃ of insulation reaction 60 minutes.Reaction finishes, and is cooled to 80 ℃, in adding and 46 grams of discoloring agent diethyl hydroxylamines, and maintains at this temperature and stirs 20 minutes, adds 843 grams of vinylbenzene, stirs 30 minutes, is fully mixed and made into HKY-10; Holding temperature, at 60 ~ 65 ℃, adds 68 grams of benzofuranone kind antioxidants, 253 grams of phosphite ester kind antioxidants, fully stirs 30 minutes, obtains the compound liquid terminator of 1# oil soluble product (1# terminator).
embodiment 2
In the 3000ml four-hole boiling flask that agitator, thermometer, vinylbenzene dropping funnel, reflux exchanger and nitrogen ingress pipe are housed, add 750 gram 2; 6-DI-tert-butylphenol compounds, 53 grams of Witco 1298 Soft Acids, the stopper of 6.0 grams; open and stir; pass into nitrogen and do nitrogen protection; slowly be warming up to 80 ~ 85 ℃, start to drip vinylbenzene at this temperature, vinylbenzene feeding quantity is 340 grams; at the uniform velocity drip and completed in 235 ~ 240 minutes, 80 ~ 85 ℃ of insulation reaction 80 minutes.Reaction finishes, and is cooled to 60 ℃, in adding and 38 grams of discoloring agent diethyl hydroxylamines, and maintains at this temperature and stirs 20 minutes, adds 807 grams of Permethyl 99A. hydrocarbon, stirs 30 minutes, is fully mixed and made into HKY-10; Holding temperature, at 75 ~ 80 ℃, adds 60 grams of benzofuranone kind antioxidants, 322 grams of phosphite ester kind antioxidants, fully stirs 50 minutes, obtains the compound liquid terminator of 2# oil soluble product (2# terminator).
embodiment 3
In the 3000ml four-hole boiling flask that agitator, thermometer, vinylbenzene dropping funnel, reflux exchanger and nitrogen ingress pipe are housed, add 750 gram 2; 6-DI-tert-butylphenol compounds, 67 grams of Witco 1298 Soft Acids, the stopper of 4.5 grams; open and stir; pass into nitrogen and do nitrogen protection; slowly be warming up to 117 ~ 120 ℃, start to drip vinylbenzene at this temperature, vinylbenzene feeding quantity is 378 grams; at the uniform velocity drip and completed in 210 ~ 215 minutes, 117 ~ 120 ℃ of insulation reaction 60 minutes.Reaction finishes, and is cooled to 70 ℃, in adding and 60 grams of discoloring agent diethyl hydroxylamines, and maintains at this temperature and stirs 30 minutes, adds 800 grams of α-vinyl toluenes, stirs 30 minutes, is fully mixed and made into HKY-10; Holding temperature, at 50 ~ 55 ℃, adds 80 grams of benzofuranone kind antioxidants, 400 grams of phosphorous acid esters antioxygens, fully stirs 60 minutes, obtains the compound liquid terminator of 3# oil soluble product (3# terminator).
embodiment 4
In the 3000ml four-hole boiling flask that agitator, thermometer, vinylbenzene dropping funnel, reflux exchanger and nitrogen ingress pipe are housed, add 750 gram 2; 6-DI-tert-butylphenol compounds, 75 grams of Witco 1298 Soft Acids, the stopper of 1.5 grams; open and stir; pass into nitrogen and do nitrogen protection; slowly be warming up to 105 ~ 108 ℃, start to drip vinylbenzene at this temperature, vinylbenzene feeding quantity is 416 grams; at the uniform velocity drip and completed in 180 ~ 185 minutes, 105 ~ 108 ℃ of insulation reaction 70 minutes.Reaction finishes, and is cooled to 80 ℃, in adding and 75 grams of discoloring agent diethyl hydroxylamines, and maintains at this temperature and stirs 20 minutes, adds 878 grams of vinylbenzene, stirs 30 minutes, is fully mixed and made into HKY-10; Holding temperature, at 60 ~ 65 ℃, adds 70 grams of benzofuranone kind antioxidants, 175 grams of phosphorous acid esters antioxygens, fully stirs 40 minutes, obtains the compound liquid terminator of 4# oil soluble product (4# terminator).
comparative example 1
3% ATSC alkali aqueous solution, had both contrasted 1# terminator.
comparative example 2
The mixture of 10% dihydroxyphenyl propane ethanolic soln, had both contrasted 2# terminator
Two,
terminator product of the present invention is effect evaluation experimental in the universal polyvinyl chloride (PVC) RESINS of suspension method
Evaluate the stabilization effect of the present invention 1 ~ 4# terminator in the universal polyvinyl chloride (PVC) RESINS of suspension method;
1, experimental raw
Still release agent (Italy is yellow, NOXOL WSW); Synthetic Co., Ltd. of dispersion agent KH-20, L-10(Japan), HPMC(The Dow Chemical Co. (US) 2030 Dow Center, Abbott Road, Midland, Michigan 48640); Initiator EHP is peroxy dicarbonate two (2-ethylhexyl) ester both), both peroxidation neodecanoic acid isopropyl phenyl esters (Nobel Aksu, Tianjin company limited) of Tx99; The present invention 1 ~ 4# terminator; Other raw material, as: vinylchlorid; Bicarbonate of ammonia; Acetone semicarbazone thiocarbamide; Dihydroxyphenyl propane is commercially available prod, and specification is industrial top grade product.
, prepare sample (1 ~ 4# sample, control sample 1#)
In 10 liters of reactors that double-deck trilobed wheel type agitator and double jacket are housed, carry out in advance antiseized still processing, then add 4350 grams of deionized waters; 0.47 gram, bicarbonate of ammonia; 2.8 grams of the KH-20 aqueous solution of working substance content 20%, 8.1 grams of the L-10 aqueous solution of working substance content 20%, 20 grams of the HPMC aqueous solution of working substance content 1%; Active matter content is 3.63 grams of 40% EHP water miscible liquids, 1.09 grams of the Tx99 water miscible liquids that active matter content is 40%.Being evacuated to still pressure is-0.095MPa, keep pressure after 5 minutes, add 3000 grams of vinylchlorid (VCM) monomers, with mixing speed 300rpm, stir 15 minutes, fully material in mixing kettle, then pass into hot water to jacket of polymerization, with 20 ~ 25 minutes, while making temperature in the kettle reach 57 ℃, reacting kettle inner pressure is 0.83-0.88 MPa, and polymerization starts timing.Polyreaction is carried out 15 minutes, at the uniform velocity amount with 400 Grams Per Hours adds 1400 grams of water in reactor, control 0.1 ℃ of still interior reaction temperature fluctuation range, reaction carry out 5 ~ 5.5 hours, transformation efficiency be about 80%, start to add terminator, continue to stir 5 minutes at 56 ~ 58 ℃, discharging, centrifuge dehydration, be dried, sieve, obtain polyvinyl chloride resin sample and control sample, various terminators can complete satisfied termination effect to polyreaction.
With aforesaid method, replace and use the present invention's 1 ~ 4# terminator and contrast 1 ~ 2# terminator, make respectively 1# sample, 2# sample, 3# sample, 4# sample and control sample 1#, control sample 2#.
, experimental technique
employing standard, " GB/T 15595 polyvinyl chloride (PVC) RESINS thermostability experimental technique whiteness methods "; " GB-T 2913-1982 plastics whiteness test method "; Whiteness and the ageing whiteness of measuring 1 ~ 4# sample, control sample 1#, further illustrate the present invention.
, experimental result
Whiteness and the ageing whiteness of table 1,1 ~ 4# sample and control sample
Experimental result shows, the ATSC, the terminator that dihydroxyphenyl propane is prepared that use the compound liquid terminator of oil soluble of the present invention and conventional art to use, whiteness to prepared polyvinyl chloride tree is variant, but ageing whiteness is apparently higher than the latter, the ageing resistance that represents terminator of the present invention is better than acetone semicarbazone thiocarbamide and dihydroxyphenyl propane, prepare the terminator in universal polyvinyl chloride resin Product Process process using this as suspension method, in polymerization process, add, obtain the polyvinyl chloride resin product with stability, improved ageing whiteness.
Claims (9)
1. a preparation method for polyvinyl chloride resin terminator, is characterized in that carrying out according to following step:
(1) prepare HKY-10: take 2,6 di t butyl phenol as raw material, vinylbenzene is alkylating reagent; Employing organic acid compound is catalyzer, add a small amount of stopper, carry out catalytic alkylation reaction generation with 2,6-di-t-butyl-4-(1-phenylethyl) the phenol liquid mixture that is principal product, after reaction finishes, cooling, in adding and discoloring agent, organic solvent, fully stir, make the phenylethyl with 2,6-di-t-butyl-4-(1-) phenol be principal product liquid antioxidant product, i.e. HKY-10;
(2) HKY-10 is added in reactor in proportion successively with a kind of benzofuranone kind antioxidant and a kind of phosphite ester kind antioxidant, stir, be warming up to 50 ~ 80 ℃, fully stir 30 ~ 60 minutes, make the compound liquid terminator of oil soluble product;
Described proportioning raw materials is 2,6 di t butyl phenol: cinnamic mol ratio is 1:0.60 ~ 2.0;
Described in step (1), the addition of catalyzer shows take 2,6 di t butyl phenol: the mass ratio of catalyzer is 1:0.02 ~ 0.2,
The addition of the stopper described in step (1) shows take 2,6 di t butyl phenol: the mass ratio of stopper is 1:0.001-0.020.
2. the preparation method of a kind of polyvinyl chloride resin terminator according to claim 1, is characterized in that the catalyzer described in step (1) is Witco 1298 Soft Acid, hexadecyl Phenylsulfonic acid, octadecyl Phenylsulfonic acid, two Witco 1298 Soft Acid, double hexadecyl Phenylsulfonic acid, two octadecyl Phenylsulfonic acid, decyl phenyl ether disulfonic acid, dodecyl diphenyl oxide disulfonic acid, hexadecyl phenyl ether disulfonic acid, two dodecyl diphenyl oxide disulfonic acid or double hexadecyl phenyl ether disulfonic acid;
Stopper described in step (1) is 2,6-di-t-butyl-4-methylphenol; 2,2 '-ethylene two (4,6-di-tert-pentyl phenol); 2,2 '-ethylene two (4,6-DI-tert-butylphenol compounds); 2,2 '-methylene-bis (4,6-di-tert-pentyl phenol); 2,2 '-methylene-bis (4,6-DI-tert-butylphenol compounds); 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol); 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol);
β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) the positive octadecyl ester of propionic acid, four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, phosphorous acid (three nonyl phenyl) ester, diphosphorous acid pentaerythritol stearic acid ester 2, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites or two (different tridecanol base) pentaerythritol diphosphites;
In described in step (1), refer to discoloring agent: aminated compounds and Na
2cO
310H
2the mixture of O; Aminated compounds is diethylamine; Triethylamine; Dipropyl amine; Tripropyl amine; Trioctylamine; Quadrol; 1,2-propylene diamine; N-hydroxyethyl-ethylenediamine; N, N-dimethylethanolamine; N, N-diethylethanolamine; Dimethyl hydroxylamine; Diethyl hydroxylamine; N-isopropylhydroxyla; Diethanolamine; Trolamine; One in diisopropanolamine (DIPA) or tri-isopropanolamine;
Organic solvent described in step (1) is vinylbenzene; α-vinyl toluene; C
10~ C
16straight-chain paraffin or isoparaffin.
3. the preparation method of a kind of polyvinyl chloride resin terminator according to claim 2, is characterized in that the proportioning raw materials described in step (1) is 2,6 di t butyl phenol: cinnamic mol ratio is 1:0.80 ~ 1.2;
Described in step (1), the addition of catalyzer shows take 2,6 di t butyl phenol: the mass ratio of catalyzer is 1:0.07 ~ 0.1;
The addition of the stopper described in step (1) shows take 2,6 di t butyl phenol: the mass ratio of stopper is 1:0.002-0.008.
4. the preparation method of a kind of polyvinyl chloride resin terminator according to claim 1, is characterized in that the temperature of reaction described in step (1) is 80-120 ℃; Under temperature of reaction, adopt vinylbenzene to drip continuously feeding manner and react with 2,6 di t butyl phenol, it is 180 ~ 240 minutes that vinylbenzene drips feed time; After charging completes, under temperature of reaction, selecting the insulation reaction time is 60 ~ 80 minutes;
The cooling that step (1) is described, selecting cooling temperature is 60 ~ 80 ℃, in adding and discoloring agent, and maintains at this temperature and stirs 20 ~ 30 minutes;
In described in step (1) and discoloring agent add-on by the mass ratio of itself and 2,6 di t butyl phenol, 2,6 di t butyl phenol: mass ratio=1:0.01 ~ 0.10 of aminated compounds; In and discoloring agent in Na
2cO
310H
2o add-on is by itself and the molar ratio computing of organic acid catalyst, selection Na
2cO
310H
2o: the mol ratio=1:2 of Witco 1298 Soft Acid;
Organic solvent add-on described in step (1) is by itself and generation 2,6-di-t-butyl-4-(1-phenylethyl) the mass ratio meter of the phenol liquid mixture that is principal product, select to generate 2,6-di-t-butyl-4-(1-phenylethyl) the phenol liquid mixture that is principal product: mass ratio=1:0.6 ~ 0.7 of organic solvent.
5. the preparation method of a kind of polyvinyl chloride resin terminator according to claim 4, it is characterized in that described in step (1) in and discoloring agent add-on by itself and 2, the mass ratio meter of 6-DI-tert-butylphenol compounds, 2,6 di t butyl phenol: the mass ratio of aminated compounds is 1:0.05 ~ 0.10.
6. the preparation method of a kind of polyvinyl chloride resin terminator according to claim 1, is characterized in that the benzofuranone kind antioxidant described in step (2) is 5,7-di-t-butyl-3-(4-methyl), 3 hydrogen-benzofuran-2-ones; 5,7-di-t-butyl-3-(3,4-dimethyl), 3 hydrogen-benzofuran-2-ones; 5,7-di-t-butyl-3-(2,4-dimethyl) 3 hydrogen-benzofuran-2-ones or 5,7-di-t-butyl-3-(2,3-dimethyl), 3 hydrogen-benzofuran-2-ones;
Phosphite ester kind antioxidant described in step (2) is that structural formula is as follows with the phosphite ester compound of Spirocyclic structure:
Making in the compound liquid terminator of oil soluble product process described in step (2), the mixing ratio of three kinds of oxidation inhibitor is measured take the organic solvent in HKY-10 as benchmark, wherein: the mass ratio of the organic solvent in HKY-10 and a kind of benzofuranone kind antioxidant is 1:0.001 ~ 0.3, the organic solvent in HKY-10 and a kind of mass ratio of phosphite ester kind antioxidant are: 1:0.01 ~ 1.2.
7. the preparation method of a kind of polyvinyl chloride resin terminator according to claim 6, is characterized in that the phosphite ester kind antioxidant described in step (2) is for two (different tridecanol base) pentaerythritol diphosphites; Two (phenylcarbinol base) pentaerythritol diphosphites; Two (lauryl alcohol base) pentaerythritol diphosphites; Two (hexadecanol base) pentaerythritol diphosphites or two (stearyl alcohol base) pentaerythritol diphosphites.
8. the preparation method of a kind of polyvinyl chloride resin terminator according to claim 6, is characterized in that in step (2) wherein: the mass ratio of the organic solvent in HKY-10 and a kind of benzofuranone kind antioxidant is 1:0.08 ~ 0.10; Organic solvent in HKY-10 and a kind of mass ratio of phosphite ester kind antioxidant are 1:0.2 ~ 0.5.
9. the using method of a polyvinyl chloride resin terminator, it is characterized in that preparing in universal polyvinyl chloride resin Product Process process in known method, the terminator product of selecting vinyl chloride monomer transformation efficiency to add the preparation method of a kind of polyvinyl chloride resin terminator in claim 1 to obtain during 70 ~ 85%, add-on is pressed into 0. 05 ~ 0.08% of still vinyl chloride monomer massfraction.
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| CN103012483A (en) * | 2012-12-04 | 2013-04-03 | 浙江海普顿新材料股份有限公司 | Phenol-free phosphite ester, as well as preparation method and application thereof |
| CN103288988B (en) * | 2013-06-19 | 2016-08-17 | 常州大学 | Styrol bisphenol-a derivative is as the preparation method of polrvinyl chloride terminator |
| CN103435725B (en) * | 2013-09-04 | 2015-10-21 | 武汉开元化学助剂有限公司 | Aqueous emulsion type polyvinyl chloride (PVC) RESINS terminator and preparation method thereof |
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