CN103288988B - Styrol bisphenol-a derivative is as the preparation method of polrvinyl chloride terminator - Google Patents
Styrol bisphenol-a derivative is as the preparation method of polrvinyl chloride terminator Download PDFInfo
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Abstract
Styrol bisphenol-a derivative of the present invention, as the preparation method of polrvinyl chloride terminator, belongs to synthetic material auxiliary agent technical field.In order to improve antioxidant bisphenol-A product intermiscibility in the polymer, carry out catalytic alkylation reaction with bisphenol-A and styrene and prepare styrol bisphenol-a derivative, for polrvinyl chloride (PVC) terminator.It is specifically related to styrol bisphenol-a derivative be combined with a kind of decolorising agent with liquefied blender with a kind of bisphenolmonoacryates compound with a kind of liquid sulfur ethers antioxidant with zinc Isoocatanoate, makes liquid terminator product.Present invention bisphenol-A and alkylated styrene react makes styrol bisphenol-a derivative, have that production technology is simple, raw material is easy to get, product use cost is low, be easy to the feature of industrial application, and this terminator has nontoxic, the feature of environmental protection, does not produce water pollutant.
Description
Technical field
The present invention is in order to improve antioxidant bisphenol-A product intermiscibility in the polymer, the change reacted by styrol
Method is modified, to obtain styrol bisphenol-a derivative, for polrvinyl chloride (PVC) terminator.It is specifically related to benzene second
Alkylene bisphenol-a derivative compounds with other material, makes liquid PVC terminator product, belongs to synthetic material auxiliary agent technical field.
Background technology
Bisphenol-A extensively makes in synthetic material directly as antioxidant, heat stabilizer, rubber antioxidant, terminator product
With.
Bisphenol-A, chemical name: 2,2-bis-(4-hydroxy phenyl) propane.Fusing point: 157.2 DEG C, water insoluble, aliphatic hydrocarbon, molten
In acetone, ethanol, methanol, ether, ethyl acetate and sig water, it is slightly soluble in toluene etc..Due to the dissolubility feature of bisphenol-A, make
Using in the polymer for antioxidant, the compatibility with various polymer is poor, easy bloom, precipitation and reduce its non-oxidizability
Energy.Bisphenol-A product refer in particular to into following formula ():
()
Bisphenol-A, as radical reaction produced in the antioxidant of hydrogen donor type, with polymeric material, had both had the strongest
Capture polymer in effect of living radical.Single electron in the benzene oxygen-derived free radicals generated with free radical reaction course can
π system big with aromatic ring is conjugated, and has many resonant structures, the most further with alkyl diradical (RO) addition, ultimately generates
More stable free radical and reach antioxidative purpose.In fact bisphenol-A is also free radical capture type antioxidant simultaneously, Er Qiefen
Having two phenyl ring and two active hydrogen atoms in son, molecular structure is analogous to bisphenol compound antioxidant, but antioxidation
Usefulness but can not show a candle to bisphenol compound antioxidant, and one of its reason is poor caused with the compatibility of polymer.
CN 1042171 discloses one and prepares hot melt high-molecular coating glue with ethylene-vinyl acetate copolymer for raw material
Its application, wherein add bisphenol-A antioxidant or thioether kind antioxidant.
CN 102229731A discloses CPVC sheet material and production technology thereof, with CPVC resin, modified ABS resin as raw material,
Adding compound rare-earth heat stabilizer and bisphenol-A antioxidant, extruded, plasticizing, molding prepare.
CN 102532750A、CN 102585399A、CN 102585400A、CN 102604260A、CN 102746671A
Disclosing the preparation method of a kind of polyvinyl chloride resin cable jacket material, wherein bisphenol-A is as heat resistanceheat resistant, the additive of oxygen.
The terminator product preparing universal polyvinyl chloride resin with bisphenol-A directly as suspension method at present is the most universal.
CN 102432715A discloses the preparation method of a kind of polyvinyl chloride polymerization special emulsion type terminator, and it uses
Diisooctyl phenyl phosphite, acetone contracting thiosemicarbazones, bisphenol-A, α-methyl styrene, tetramethylolmethane are that raw material is made.Its
It is disadvantageous in that: the particle that acetone contracting thiosemicarbazones, bisphenol-A are ground to form 70 ~ 90 mesh by colloid mill is distributed to liquid
Middle composition suspension, it is clear that the acetone contracting thiosemicarbazones of the particle of 70 ~ 90 mesh and bisphenol-A are difficult to be dissolved in resin, its fall
Low acetone contracting thiosemicarbazones and the effective utilization of bisphenol-A.
CN101921354A discloses the preparation method of the high Corvic of a kind of transparency, wherein with 1:1 bisphenol-A and
Sulfur is for malonic acid lauryl；1:1 antioxidant 1010 and sulfur are for malonic acid lauryl；1:0.6 antioxidant BHT and sulfur are for the malonic acid moon
Osmanthus ester is compounding as compound terminator.It is disadvantageous in that: solid matter bisphenol-A, antioxidant 1010, BHT, sulfur are for malonic acid
Lauryl is difficult to dispersion and dissolves in polyvinyl chloride resin, greatly reduces the effective utilization of antioxidant.
CN 101041729 discloses one (PVC) nontoxic calcium zinc heat stabilizer composition and preparation method thereof, uses fat
Fat acid zinc and fatty acid calcium are base stock, compound with bisphenol-A antioxidant, make nontoxic calcium zinc composite thermal stabilizer, and it is not enough
Part is: the dosage form of final products is pressed powder.
CN 101775153A discloses one (PVC) barium-zinc liquid stabilizer and its preparation method and application, uses different pungent
Acid zinc and isooctyl acid barium are base stock, compound with antioxidant bisphenol-A and make liquid stabilisers.It is disadvantageous in that: bisphenol-A
Fusing point is high, and the compatibility with polymer P VC resin is poor.
Use during suspension method prepares universal polyvinyl chloride resin, need when polyreaction reaches certain conversion ratio and
Time add terminator and terminate the continuity of polyreaction, heat stabilizer to be added improves the ageing whiteness of PVC product.
Antioxidant bisphenol-A is a kind of inexpensive raw material.Bisphenol-A fusing point is high, containing double hydroxyls, dissolves in aliphatic hydrocarbon and aromatic hydrocarbon
Spending very poor, the compatibility with polymer P VC resin is poor, by the alkylated reaction of bisphenol-A, rationally introduces at hydroxyl ortho position and is subject to
Resistance alkane group, makes bisphenol-A alkyl derivative, can substantially increase its oil-soluble, improve bisphenol-A alkyl derivative with
The compatibility of polymer, it addition, introduce the bisphenol-a derivative of the alkane group that is obstructed, compared with bisphenol-A itself, raw for it
The benzene oxygen-derived free radicals stability become improves, and its antioxygenic effect improves, and the antioxygenic property of alkylated bisphenols A derivant is better than double
Phenol A.
Summary of the invention
Directly using the defect existing for antioxidant bisphenol-A to improve conventional art, the present invention is with styrene and bisphenol-A
Carry out catalytic alkylation reaction, make styrol bisphenol-a derivative, with zinc Isoocatanoate and a kind of liquid sulfur ethers antioxidant with
A kind of bisphenolmonoacryates compound is combined with a kind of decolorising agent with liquefied blender, makes liquid terminator product,
The terminator of universal polyvinyl chloride resin is prepared, to improve the ageing whiteness of polyvinyl chloride resin product as suspension method.
Styrol bisphenol-a derivative of the present invention is as the preparation method of polrvinyl chloride terminator, according to following step
Suddenly carry out:
Styrol bisphenol-a derivative is prepared for raw material, after reaction terminates, by temperature in the kettle control with bisphenol-A, styrene
75 ~ 80 DEG C, by liquefied blender and a kind of liquid sulfur ethers antioxidant and zinc Isoocatanoate and a kind of bisphenolmonoacryates
Compound is proportionally added in styrol bisphenol-a derivative with a kind of decolorising agent, is sufficiently stirred for 30 ~ 40 minutes, makes reactor
Interior material dissolution is uniform, is cooled to 20 ~ 25 DEG C, makes fluid present invention terminator product.
Wherein said liquid sulfur ethers antioxidant refers to methylene bis isooctyl thioglycolate, and molecular formula is [CH2(S
CH2COO C8H17) 2] (being called for short: double sulphur compounds), double sulphur compounds are that styrol bisphenol-a derivative is very effective molten
Agent.
Wherein said zinc Isoocatanoate refers to the zinc Isoocatanoate that Zn content (mass content) is 6% or 12%.
Wherein said liquefied blender refers to diisooctyl phthalate or dehydrated alcohol.
Wherein said bisphenolmonoacryates compound refers to 2-[1-(2-hydroxyl-3,5-di-tert-butyl
Base)-methyl]-4,6-di-tert-butyl-phenyl acrylate (abbreviation: antioxidant MA) 2-[1-(2-hydroxyl-3,5-two tert-amylbenzene
Base)-ethyl]-4,6-two tertiary amyl phenyl acrylate (being called for short: antioxidant GS)；2-tertiary butyl-6-(3-tertiary butyl-2-hydroxyl
Base-5-aminomethyl phenyl)-4-methylphenol acrylate (abbreviation: antioxidant GM).
Wherein said various material additional proportions are counted in mass ratio, bisphenol-A: double sulphur compound=1:1.06-2.21；Double
Phenol A: zinc Isoocatanoate=1:1.67-2.12；Bisphenol-A: bisphenolmonoacryates compound=1:0.131-0.291；Bisphenol-A: liquid
State blender=1:4.2-4.6；Bisphenol-A: decolorising agent=1:0.04-0.21
Wherein said styrol bisphenol-A refer to by following formula (), (), () material is main component institute group
The mixture become.Using liquid chromatograph, area normalization method analysis, the mass content of each material has the feature that
Bisphenol-A % :≤2.0
Two substitution product %(): 65.0-75.0
One substitution product %(): 15.0-20.0
Trisubstitution product %(): 2.0-3.0
Other unknown material: 5.0-10
() () ()
Those skilled in the art it is easily understood that in styrol bisphenol-A with (), (), () these three
Material is main component, reacts the by-product of generation in other unknown material, including (), (), () homologue.
The preparation method of wherein said styrol bisphenol-a derivative:
Bisphenol-A, organic solvent, organic acid catalyst, phase transfer catalyst, polymerization inhibitor are proportionally added in reactor,
Making nitrogen protection, stirring heats up, at the reaction temperatures, drips styrene in proportion, carries out being catalyzed alkyl under heterogeneous state
Changing reaction, after dropping styrene terminates, insulation reaction, reaction terminates, and organic solvent is distilled off, and obtains benzene of the present invention
Vinylation bisphenol-a derivative.
Wherein said organic solvent refers to hexamethylene, isobutyltrimethylmethane., toluene；Described organic acid catalyst refers to:
Pyrovinic acid, DBSA, dodecyl diphenyl oxide disulfonic acid；Described phase transfer catalyst refers to nonyl phenol and gathers
Oxygen vinyl Ether, trade name TX-8；Described polymerization inhibitor is 2,6-di-t-butyl-4-methylphenol, 2,2 '-ethylene double (4,
6-di-tert-pentyl phenol), 2,2 '-ethylene double (4,6-DI-tert-butylphenol compounds), four (β-(3,5-di-tert-butyl-hydroxy phenyls)
Propanoic acid) pentaerythritol ester, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, double (2,4-di-tert-butyl-phenyl) tetramethylolmethane two be sub-
Phosphate ester；Described decolorising agent refers to N, N-diethyl hydroxylamine.
Wherein said inhomogeneous reaction refers to: bisphenol-A raw material can not melt at the reaction temperatures, can not be dissolved in
In organic solvent, but it is mixed in organic solvent with solid forms, under the heterogeneous state of solid, liquid, carries out catalytic alkylation anti-
Should, until reaction of styrene bisphenol-a derivative.
Wherein said proportioning raw materials is: bisphenol-A: styrene (mol ratio)=1:1.5-2.0；Bisphenol-A: organic acid catalysis
Agent (mass ratio)=1:0.02-0.04；Bisphenol-A: organic solvent (mass ratio)=1:2.0；Bisphenol-A: phase transfer catalyst (matter
Amount ratio)=1:0.004 ~ 0.012；Bisphenol-A: polymerization inhibitor (mass ratio)=1:0.004-0.025；
Wherein said stirring warming temperature is 70-95 DEG C；At the reaction temperatures, styrene drips charging, benzene second continuously
Alkene dropping feed time is 240-280 minute；After having fed, at the reaction temperatures, selecting the insulation reaction time is 60 minutes.
Styrol bisphenol-a derivative of the present invention refer in particular to into above formula (), (), () three kinds of materials are main
Want composition with phase transfer catalyst, polymerization inhibitor, the mixture of decolorising agent.
The present invention is one styrol bisphenol-a derivative and zinc Isoocatanoate and a kind of liquid sulfur ethers antioxidant and one
Bisphenolmonoacryates compound is combined with liquefied blender, makes liquid terminator product, logical as suspension method preparation
With the terminator of type polyvinyl chloride resin, select Vinyl Chloride Monomer conversion ratio to add the terminator product of the present invention during 70-85%, add
Enter amount and be pressed into 0. 07-0.08% of still Vinyl Chloride Monomer mass fraction, to improve the ageing whiteness of polyvinyl chloride resin product.
Advantages of the present invention
1, the present invention is reacted with alkylated styrene by bisphenol-A, rationally introduces the alkane group that is obstructed at hydroxyl ortho position, system
Become styrol bisphenol-A, increase its oil-soluble, improve the compatibility of bisphenol-a derivative and polymer, it addition, introduce the alkane that is obstructed
The bisphenol-a derivative of hydrocarbyl group, will have further raising for its benzene oxygen-derived free radicals stability generated, improve its antioxidation
Usefulness and the polyvinyl chloride resin compatibility, be uniformly dispersed in the PVC product of porous particle and be difficult to volatilization loss.
2, the present invention is double with one with a kind of liquid sulfur ethers antioxidant with zinc Isoocatanoate with styrol bisphenol-a derivative
Phenol mono acrylic ester compounds is combined, and makes liquid terminator product, prepares universal polyvinyl chloride resin product as suspension method
Terminator, to obtain the polyvinyl chloride resin product with stability, improves ageing whiteness.
3, present invention bisphenol-A and alkylated styrene react and make styrol bisphenol-a derivative, have production technology
Simply, raw material is easy to get, product use cost is low, be easy to the feature of industrial application, and this terminator has nontoxic, ring
The feature protected, does not produce water pollutant.
Detailed description of the invention
All raw materials used in the present invention, such as: bisphenol-A, styrene, organic solvent, organic acid catalyst, phase transfer are urged
The zinc Isoocatanoate of agent, polymerization inhibitor, 12% or 6%, diisooctyl phthalate, dehydrated alcohol, isooctyl thioglycolate, 37%
Formalin, diethyl hydroxylamine, antioxidant GS are commercially available prod, and specification is industry top grade product.
Methylene bis isooctyl thioglycolate preparation method of the present invention:
Equipped with agitator, reflux condensation mode water knockout drum, thermometer 500mL there-necked flask in add isooctyl thioglycolate
100g, 37% formalin 95.4g, hexamethylene 100g, pyrovinic acid 1.0g, stirring is warming up to 79-81 DEG C, at this temperature
Carry out back flow reaction, meanwhile, from reactant liquor, constantly deviate from water by reflux condensation mode water knockout drum, back flow reaction 4.0h,
Reaction completes, and reactant liquor is cooled to 25-35 DEG C, and it is close neutral to reactant liquor that washing removes acidic catalyst, is distilled off anti-
Answer the hexamethylene in liquid, obtain white or the transparent liquid of off-white color, both methylene bis isooctyl thioglycolates.
Following non-limiting example 1-3 or comparative example 1-2 are used for illustrating the present invention rather than to the present invention
Limit, in the spirit of the present invention and the protection domain of claim, any modifications and changes that the present invention is made, all
Belong to protection scope of the present invention.
One, prepared by fluid present invention terminator product
Embodiment 1
In the reaction bulb equipped with agitator, thermometer, styrene Dropping funnel, reflux condenser and nitrogen ingress pipe,
Add 25.0g bisphenol-A, 50g hexamethylene, 1.0g DBSA, four (β-(3, the 5-di-t-butyl-4-hydroxy benzeness of 0.1g
Base) propanoic acid) pentaerythritol ester, 0.2g NPE, open stirring, be passed through nitrogen make nitrogen protection, slowly heat up
To 70 DEG C, starting to drip styrene at this temperature, styrene feeding quantity is 28.0g, at the uniform velocity drips and in 260 minutes
Complete, 70 DEG C of insulation reaction 60 minutes.Reaction terminates, and decompression distills out whole hexamethylene, maintains temperature 78 ~ 80 DEG C, (repaiies
Change) add the double sulphur compound of 26.5g, 82g Zn content be 12% zinc Isoocatanoate, 5g antioxidant 2-[1-(2-hydroxyl-3,5-two
Tertiary amyl phenyl)-ethyl]-4,6-bis-tertiary amyl phenyl acrylate, 106g dehydrated alcohol, it is cooled to 40 ~ 50 DEG C, adds
1.0g diethyl hydroxylamine, is cooled to room temperature, makes fluid present invention terminator product (1# terminator), working substance content
50.6%。
Embodiment 2
In the reaction bulb equipped with agitator, thermometer, styrene Dropping funnel, reflux condenser and nitrogen ingress pipe,
Add 22.8g bisphenol-A, 45.6g toluene, 0.46g DBSA, four (β-(3, the 5-di-t-butyl-4-hydroxyls of 0.5g
Phenyl) propanoic acid) pentaerythritol ester, 0.1g NPE, open stirring, be passed through nitrogen make nitrogen protection, slowly rise
Temperature, to 90 DEG C, starts to drip styrene at this temperature, and styrene feeding quantity is 30.3g, at the uniform velocity drips and at 240 minutes
Inside complete, 95 DEG C of insulation reaction 60 minutes.Reaction terminates, and decompression distills out whole toluene, maintains temperature 78 ~ 80 DEG C, adds 40g
Double sulphur compounds, 140g Zn content be 6% zinc Isoocatanoate, 3g antioxidant 2-[1-(2-hydroxyl-3,5-two tertiary amyl phenyl)-
Ethyl]-4,6-bis-tertiary amyl phenyl acrylate, 106g diisooctyl phthalate, it is cooled to 40 ~ 50 DEG C, adds 3.0g
Diethyl hydroxylamine, is cooled to room temperature, makes fluid present invention terminator product (2# terminator), working substance content 41.7%.
Embodiment 3
In the reaction bulb equipped with agitator, thermometer, styrene Dropping funnel, reflux condenser and nitrogen ingress pipe,
Add 24g bisphenol-A, 48g isobutyltrimethylmethane., 0.7g DBSA, four (β-(3, the 5-di-t-butyl-4-hydroxy benzeness of 0.6g
Base) propanoic acid) pentaerythritol ester, 0.3g NPE, open stirring, be passed through nitrogen make nitrogen protection, slowly heat up
To 90 DEG C, starting to drip styrene at this temperature, styrene feeding quantity is 29g, at the uniform velocity drips and complete in 220 minutes
Become, 90 DEG C of insulation reaction 60 minutes.Reaction terminates, and decompression distills out whole isobutyltrimethylmethane., maintains temperature 78 ~ 80 DEG C, adds 53g
Double sulphur compounds, 62g Zn content be 12% zinc Isoocatanoate, 7g antioxidant 2-[1-(2-hydroxyl-3,5-two tertiary amyl phenyl)-
Ethyl]-4,6-bis-tertiary amyl phenyl acrylate, 106g dehydrated alcohol, it is cooled to 40 ~ 50 DEG C, adds 5.0g diethyl hydroxyl
Amine, is cooled to room temperature, makes fluid present invention terminator product (3# terminator), working substance content 53.4%.
Comparative example 1
In the reaction bulb equipped with agitator, thermometer, styrene Dropping funnel, reflux condenser and nitrogen ingress pipe,
Add 25.0g bisphenol-A, 50g hexamethylene, 1.0g DBSA, four (β-(3, the 5-di-t-butyl-4-hydroxy benzeness of 0.1g
Base) propanoic acid) pentaerythritol ester, 0.2g NPE, open stirring, be passed through nitrogen make nitrogen protection, slowly heat up
To 80 ~ 82 DEG C, starting to drip styrene at this temperature, styrene feeding quantity is 28.0g, at the uniform velocity drips and at 260 points
Complete in clock, 80 ~ 82 DEG C of insulation reaction 60 minutes.Reaction terminates, and decompression distills out whole hexamethylene, maintains temperature 78 ~ 80 DEG C,
Add the zinc Isoocatanoate 106g dehydrated alcohol that 82g Zn content is 12%, be cooled to 40 ~ 50 DEG C, add 1.0g diethyl hydroxylamine,
It is cooled to room temperature, obtains 2# and contrast terminator, working substance content 44.0%.
Comparative example 2
In reaction bulb, add zinc Isoocatanoate, 106g dehydrated alcohol that 53g bisphenol-A, 82g Zn content are 12%, 40 ~
Stir at 50 DEG C, dissolve, add 1.0g diethyl hydroxylamine, be down to room temperature, obtain 2# and contrast terminator, working substance content 44.0%.
Two, terminator product of the present invention application effect appraisal experiment in the universal Corvic of suspension method
Evaluate 1-3# terminator of the present invention, the 1-2# contrast stabilisation effect in the universal Corvic of suspension method
Really；
1, experimental raw
Anti-fouling agent (Italy is yellow, NOXOL WSW)；Dispersant KH-20, L-10(Japan synthesizes Co., Ltd.), HPMC
(The Dow Chemical Co. (US) 2030 Dow Center, Abbott Road, Midland, Michigan 48640)；Initiator EHP both peroxy dicarbonate two (2-ethylhexyl) esters), Tx99 both peroxidating neodecanoic acids
Isopropyl phenyl ester (Nobel Aksu, Tianjin company limited)；Other raw material, such as: vinyl chloride；Ammonium hydrogen carbonate；Acetone semicarbazone sulfur
Urea；Bisphenol-A is commercially available prod, and specification is industry top grade product.
, prepare sample (1-3# sample, control sample 1-3#)
Use 7m3Polyvinyl chloride polymerization reactor prepares 1# sample, 2# sample, 3# sample and control sample 1#, to having a competition
Sample 2#, contrasts terminator to 1-3# terminator of the present invention and 1-2# simultaneously and carries out performance evaluation.
Operating process is fed and discharging accordingly by the pipeline being installed on polymeric kettle and each pans, polymeric kettle
It is in air-tight state, first carries out antiseized still process, evacuation nitrogen displacement.Add ammonium hydrogen carbonate 0.40 kilogram；85 DEG C
Deionized water 3000 kilograms；Vinyl chloride (VCM) monomer 2500 kilograms；The KH-20 aqueous solution of working substance content 20% 2.0 kilograms, has
The L-10 aqueous solution 5.96 kilograms of effect thing content 20%, the HPMC aqueous solution of working substance content 1% 1.41 kilograms.It is sufficiently stirred for, adjusts
Saving and maintain temperature in the kettle at 56 ~ 57 DEG C, reacting kettle inner pressure is 0.85 ~ 0.87MPa, and adding active matter content is the EHP of 20%
Aqueous emulsion 5.26 kilograms, active matter content is the Tx99 aqueous emulsion 1.56 kilograms of 20%.It is thoroughly mixed in still material and maintains
Temperature in the kettle is at 56 ~ 57 DEG C, after polyreaction carries out 10 minutes, goes toward adding in reactor with the at the uniform velocity amounts of 90 kgs/hour
Ionized water, controls still interior reaction temperature fluctuation range 0.1 DEG C, and reaction is carried out 4.8 ~ 5.0 hours, in still pressure be 0.58 ~
0.62MPa, is initially added into terminator, stirs 20 minutes at 56 ~ 57 DEG C.Cooling discharge, centrifuge dehydration, it is dried, sieves, obtain
Polyvinyl chloride resin sample and control sample.
Method described above, replaces and uses 1-3# terminator of the present invention and 1-2# to contrast terminator, be respectively prepared 1# sample,
2# sample, 3# sample and control sample 1#, control sample 2#.
, terminator is on sample whiteness and the impact of ageing whiteness
Employing standard, " GB/T 15595 Corvic heat stability experimental technique whiteness method "；《GB-T 2913-
1982 plastics whiteness test methods "；Measure 1-3# sample, the whiteness of control sample 1-2# and ageing whiteness, further illustrate
The present invention, experimental result is as shown in table 1.
Table 1 1-3# sample and the whiteness of control sample 1-2# and ageing whiteness
Test result indicate that, use the whiteness of 1-3# sample prepared by terminator of the present invention and ageing whiteness to be better than contrast
Sample 1-2#, prepares the terminator in universal polyvinyl chloride resin technical process in this, as suspension method, it is thus achieved that have stability
Polyvinyl chloride resin product, improve ageing whiteness.The whiteness of control sample 1# and ageing whiteness be better than control sample 2# whiteness and
Ageing whiteness, shows that the ageing resistace preparing terminator for raw material with styrol bisphenol-A is better than bisphenol-A.
Claims (3)
1. as the preparation method of styrol bisphenol-a derivative of polrvinyl chloride terminator, it is characterised in that:
Styrol bisphenol-a derivative is prepared for raw material with bisphenol-A, styrene, after reaction terminates, temperature in the kettle is controlled 75 ~
80 DEG C, by liquefied blender and a kind of liquid sulfur ethers antioxidant and zinc Isoocatanoate and a kind of bisphenolmonoacryates chemical combination
Thing is proportionally added in styrol bisphenol-a derivative with a kind of decolorising agent, is sufficiently stirred for 30 ~ 40 minutes, makes thing in reactor
Material is uniformly dissolved, and is cooled to 20 ~ 25 DEG C, makes liquid terminator product；Wherein said liquid sulfur ethers antioxidant refers to
Methylene bis isooctyl thioglycolate；
Wherein said zinc Isoocatanoate refers to the zinc Isoocatanoate that zinc mass content is 6% or 12%；
Wherein said liquefied blender refers to diisooctyl phthalate or dehydrated alcohol；
Wherein said bisphenolmonoacryates compound refers to 2-[1-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-first
Base]-4,6-di-tert-butyl-phenyl acrylate, 2-[1-(2-hydroxyl-3,5-bis-tertiary amyl phenyl)-ethyl]-4,6-bis-spy penta
Base phenyl acrylate；2-tertiary butyl-6-(3-tertiary butyl-2-hydroxy-5-methyl base phenyl)-4-methylphenol acrylate；
Wherein said various material additional proportions are counted in mass ratio, bisphenol-A: methylene bis isooctyl thioglycolate=1:1.06-
2.21；Bisphenol-A: zinc Isoocatanoate=1:1.67-2.12；Bisphenol-A: bisphenolmonoacryates compound=1:0.131-0.291；Double
Phenol A: liquefied blender=1:4.2-4.6；Bisphenol-A: decolorising agent=1:0.04-0.21；
Wherein said styrol bisphenol-a derivative refer to by following formula (), (), () material is main component institute
The mixture of composition；Using liquid chromatograph, area normalization method analysis, the mass content of each material has the feature that
Bisphenol-A % :≤2.0
Two substitution product %(): 65.0-75.0
One substitution product %(): 15.0-20.0
Trisubstitution product %(): 2.0-3.0
Other unknown material: 5.0-10
。
The preparation method of the styrol bisphenol-a derivative as polrvinyl chloride terminator the most according to claim 1, its
It is characterised by the preparation method of wherein said styrol bisphenol-a derivative:
Bisphenol-A, organic solvent, organic acid catalyst, phase transfer catalyst, polymerization inhibitor are proportionally added in reactor, make nitrogen
Gas shielded, stirring heats up, at the reaction temperatures, drips styrene in proportion, carry out catalytic alkylation anti-under heterogeneous state
Should, after dropping styrene terminates, insulation reaction, reaction terminates, and organic solvent is distilled off, and obtains described styrol bis-phenol
A derivant;
Wherein said organic solvent refers to hexamethylene, isobutyltrimethylmethane., toluene；Described organic acid catalyst refers to: methyl
Sulfonic acid, DBSA, dodecyl diphenyl oxide disulfonic acid；Described phase transfer catalyst refers to polyoxyethylene nonyl phenyl second
Alkene ether, trade name TX-8；Described polymerization inhibitor is 2,6-di-t-butyl-4-methylphenol, 2,2 '-ethylene double (4,6-bis-
Tert-amyl phenol), 2,2 '-ethylene double (4,6-DI-tert-butylphenol compounds), four (β-(3,5-di-tert-butyl-hydroxy phenyls) third
Acid) pentaerythritol ester, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, double (2,4-di-tert-butyl-phenyl) tetramethylolmethane two phosphorous
Acid esters；Described decolorising agent refers to N, N-diethyl hydroxylamine;
Wherein said inhomogeneous reaction refers to: bisphenol-A raw material can not melt at the reaction temperatures, it is organic to be dissolved in
In solvent, but it is mixed in organic solvent with solid forms, under the heterogeneous state of solid, liquid, carries out catalytic alkylation reaction,
Until reaction of styrene bisphenol-a derivative;
Wherein said proportioning raw materials is: ratio bisphenol-A: styrene=1:1.5-2.0；Count bisphenol-A in mass ratio: have
Machine acid catalyst=1:0.02-0.04；Count bisphenol-A in mass ratio: organic solvent=1:2.0；Count bisphenol-A in mass ratio: turn mutually
Shifting catalyst=1:0.004 ~ 0.012；Count bisphenol-A in mass ratio: polymerization inhibitor=1:0.004-0.025；
Wherein said stirring warming temperature is 70-95 DEG C；At the reaction temperatures, styrene drips charging continuously, and styrene drips
Adding feed time is 240-280 minute；After having fed, at the reaction temperatures, selecting the insulation reaction time is 60 minutes.
Styrol bisphenol-a derivative the most according to claim 1 exists as the application of polrvinyl chloride terminator, its feature
In a kind of styrol bisphenol-a derivative and zinc Isoocatanoate and a kind of liquid sulfur ethers antioxidant and a kind of diphenyl acrylate
Compounds is combined with liquefied blender, makes liquid terminator product, prepares the end of universal polyvinyl chloride resin as suspension method
Only agent, selects Vinyl Chloride Monomer conversion ratio to add the terminator product described in claim 1 during 70-85%, and addition is pressed into
0. 07-0.08% of still Vinyl Chloride Monomer mass fraction, to improve the ageing whiteness of polyvinyl chloride resin product;Wherein said raw material
Proportioning is: ratio bisphenol-A: styrene=1:1.5-2.0.
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| CN105732857A (en) * | 2016-03-17 | 2016-07-06 | 乌鲁木齐市华泰隆化学助剂有限公司 | Composite polyvinyl chloride resin oil-soluble terminator and preparation method thereof |
| CN105801728B (en) * | 2016-03-17 | 2018-03-09 | 乌鲁木齐市华泰隆化学助剂有限公司 | Molten terminator of polyvinyl chloride resin oil and preparation method thereof |
| CN106700129B (en) * | 2016-10-20 | 2018-11-23 | 北京吉海川科技发展有限公司 | A kind of esters antioxidant of sterically hindered phenol and its preparation method and application |
| CN109422857A (en) * | 2017-08-30 | 2019-03-05 | 北京彤程创展科技有限公司 | A kind of modified bisphenol phenolic resin, preparation method and application |
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