CN106893159A - A kind of preparation method of ageing whiteness toughening PVC resin high - Google Patents
A kind of preparation method of ageing whiteness toughening PVC resin high Download PDFInfo
- Publication number
- CN106893159A CN106893159A CN201610558837.7A CN201610558837A CN106893159A CN 106893159 A CN106893159 A CN 106893159A CN 201610558837 A CN201610558837 A CN 201610558837A CN 106893159 A CN106893159 A CN 106893159A
- Authority
- CN
- China
- Prior art keywords
- latex
- toughness reinforcing
- solid
- state
- hindered phenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
- C08L9/04—Latex
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention provides a kind of preparation method of ageing whiteness PVC toughened resins high.Anti-aging treatment will be carried out to toughness reinforcing latex through the solid-state hindered phenol age resistor of emulsifier, be subsequently adding in PVC slurries, toughened PVC resin is prepared in the presence of flocculant.Polyvinyl chloride resin prepared by the toughness reinforcing latex after being processed using anti-aging, its ageing whiteness is greatly improved, and also effectively increases the heat endurance and processing stability of toughened PVC resin.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of preparation of ageing whiteness toughening PVC resin high
Method.
Background technology
Presently disclosed patent is to improve poly- by the adjustment to component used in suspension polymerization of VC system
The whiteness of vinyl chloride resin, transparent or heat endurance.
A kind of aqueous suspension polymerization method of the invention of patent No. CN 1501945A there is provided vinyl chloride.Using the invention
Preparing has good white colour Corvic.In method of the present invention for vinyl chloride aqueous suspension polymerization, polymerization is drawn
Hair agent contains at least one compound selected from dialkyl peroxydicarbonates, the tertiary alkanoic acid ester of peroxide and diacyl peroxides,
Nitroxide type stable free radical has been used as polymerization terminator.
Japan Patent JP2000143710 inventions provide a kind of preparation method of Corvic, using the invention system
Standby a kind of with good transparent and fabulous heat-resisting water whitening Corvic, for producing transparent article, water is mutually deposited
In a kind of special suspension stabilizer.
Japan Patent JP51074078 provides a kind of suspension polymerized vinyl chloride.Heat endurance is prepared using the invention to improve
Polyvinyl chloride, polymerization temperature at 47-57 DEG C, polymerization catalyst include acetyl glyceryl ether phosphatidylcholine and even two-（2,4-
Dimethyl -4- methoxyl-valeronitriles）, suspension stabilizer is the vinyl acetate of the saponification of 70-78%, and saponification degree is 80-86%.It is mixed
Catalyst, stabilizer, the VCM of conjunction are polymerized 6.8 hours at 53 DEG C, and the good polyvinyl chloride of the transparency is obtained, and show
Its discoloration-resisting is good.
Japan Patent JP2024304 exists there is provided a kind of purpose of the transparent polyvinyl chloride process for preparing resins application invention
In the phosphite that polyalcohol is added in the aqueous solution of suspension polymerisation, and the partly-hydrolysed polyethylene with low saponification degree
Alcohol, prepares transparent fabulous resin after shaping. CONSTITUTION:When vinyl chloride or a vinyl
monomer containing vinyl chloride is subjected to suspension polymerization
in an aqueous medium in the presence of a partially saponified PVA having a
low degree of saponification, for example, a degree of saponification of 20-
75mol%, and preferably having a degree of polymerization of 150-750 to
produce the title resin, a phosphite of a polyhydric alcohol, preferably
having a molecular weight of 550 or more and a P content of 6wt.% or more
[eg, bis(nonylphenyl)pentaerythritol diphosphite] in an amount of 0.005-
0.3wt.% based on the title resin is added to the reaction mixture and/or the
produced resin separated from the reaction mixture at least one step before,
during or after the polymerization.
Japan Patent JP6172407 provides a kind of method for preparing Corvic, is in order in water phase using the invention
Middle addition polyethylene oxide, a kind of oil-soluble polymerization initiator and a kind of slaine suspension polymerized vinyl chloride base monomer, polymerization
Stabilization, the polyvinyl chloride transparent of generation is good, is prevented from inside reactor fouling.
United States Patent (USP) US6340729 provides a kind of chloroethylene polymerization technique of use azanol, and the invention is using single
VCM or VCM and mixture suspension polymerisation in water phase of other vinyl monomers technique, polymerization draws
Hair agent is at least selected from：Dialkyl peroxydicarbonates, in peroxidating-tert- alkanoate or diacyl peroxide one
Kind, monosubstituted or disubstituted azanol is used as terminator.Color and heat endurance that so obtained resin has had.
It is by component used in suspension polymerization of VC system more than in terms of domestic and international disclosed Patent
Adjustment come improve Corvic whiteness, the transparency or heat endurance.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of method for preparing ageing whiteness toughening PVC resin high, with
Improve the heat endurance and processing stability of polyvinyl chloride resin.
A kind of method for preparing ageing whiteness toughening PVC resin high of the present invention, it is characterised in that be to being added to PVC slurries
In toughness reinforcing latex carry out anti-aging treatment, the anti-aging processing method of toughness reinforcing latex is will at a certain temperature through emulsifying agent breast
The solid-state hindered phenol age resistor of change is well mixed in being added to toughness reinforcing latex.
Core of the invention is exactly to carry out anti-aging treatment to toughness reinforcing latex using Hinered phenols solid-state, is subsequently used for toughness reinforcing
The preparation of type polyvinyl chloride resin.
To improve the heat endurance and processing stability of toughened PVC resin, one kind that the present invention is provided prepares high aging
The method of whiteness toughening PVC resin, specific step is：By dodecyl sodium sulfate（Emulsifying agent A）, solid-state hindered phenol age resistor
264 are compounded by a certain percentage, are placed in water bath with thermostatic control after being subsequently adding suitable quantity of water, and temperature control is higher than age resistor fusing point, and
It is stirred, is added to after age resistor is completely dissolved in toughness reinforcing glue latex, and be stirred, anti-old place is carried out to NBR latex
Reason.Using anti-aging process toughness reinforcing latex according to known technique technique carry out flocculate toughening PVC resin preparation.
The present invention is applied to the system that can carry out various property modifications to PVC using water-based latex, such as uses MBS latex
To PVC anti-impacts, the improvement of processability；NBR latex is to being modified for PVC toughness etc..Toughness reinforcing can be effectively improved with the method for the present invention
The ageing whiteness of type polyvinyl chloride resin, effectively improves the heat endurance and processing stability of toughened PVC resin.Core of the invention
Anti-aging treatment exactly is carried out to toughness reinforcing latex using Hinered phenols solid-state age resistor, the system of toughened PVC resin is subsequently used for
It is standby.
The anti-aging method of toughness reinforcing latex, its formula is as follows（Mass fraction）：
NBR latex（In terms of solid content） 100
Solid-state hindered phenol antioxidant 264 3 ~ 5
Emulsifying agent A 5-15
Newborn deionized water 20 ~ 50
Acrylonitrile content is 30 ~ 40%, solid content >=40%, the NBR latex of the degree of cross linking >=70% in described toughness reinforcing latex.
Specifically preparation technology is：
（1）Emulsifying agent A, solid-state hindered phenol antioxidant 264 are weighed in the ratio to be positioned in beaker, add suitable quantity of water, application
Water bath with thermostatic control is heated and starts stirring.
（2）The emulsification system temperature is（60~90）± 5 DEG C, preferred system temperature is（70~80）±5℃.
（3）The mixing speed of the emulsification system is 100 ~ 400 minutes/turns, preferably 200 ~ 300 minutes/turn.
（4）Weigh toughness reinforcing latex.
（5）After solid-state age resistor is emulsified completely, emulsion is poured into toughness reinforcing latex and starts stirring.
（6）The speed of agitator of the preventing aging system is 100 ~ 400 minutes/turns, preferably 200 ~ 300 minutes/turn.Stirring 3 ~
It is standby after 5 minutes.
The present invention is added in PVC slurries by the toughness reinforcing latex that anti-aging is processed, and toughness reinforcing is prepared in the presence of flocculant
Type polyvinyl chloride resin.Toughened PVC resin prepared by the toughness reinforcing latex after being processed using anti-aging, its ageing whiteness is greatly improved,
Effectively increase the heat endurance and processing stability of toughened PVC resin.
Specific embodiment
With reference to embodiment, the present invention is further illustrated, but and is not so limited the present invention.
The anti-aging formula such as table 1 of toughness reinforcing latex：
The embodiment basic recipe of table 1
Emulsification treatment first is carried out to antioxidant 264 in a heated condition using emulsifying agent according to the method described in the present invention, is emulsified
Age resistor emulsion afterwards carries out anti-aging treatment to toughness reinforcing latex, is subsequently used for the preparation of toughening PVC resin.
The performance comparison of four embodiment flocculation toughening PVC resins is shown in Table 2.
The ageing whiteness performance of the flocculation toughening PVC resin of table 2
With the increase of aging inhibitor dosage, the ageing whiteness of toughened resin is stepped up, and adds 2g solid-states to receive in 50g NBR latexes
Resistance phenol age resistor is that can reach preferably to prevent old effect.Toughness reinforcing latex is prepared after being processed through the anti-aging of Hinered phenols solid-state age resistor
The ageing whiteness of polyvinyl chloride resin can be effectively improved.
Claims (5)
1. a kind of method for preparing ageing whiteness toughening PVC resin high, it is characterised in that be the toughness reinforcing to being added in PVC slurries
Latex carries out anti-aging treatment, and the anti-aging processing method of toughness reinforcing latex is by the solid-state at 30 ~ 90 DEG C through emulsifier
Hindered phenol antioxidant 264 is well mixed in being added to toughness reinforcing latex.
2. method according to claim 1, it is characterised in that solid-state hindered phenol antioxidant 264 mixes with emulsifying agent, Ran Houjia
It is placed in water bath with thermostatic control after entering suitable quantity of water, temperature control is stirred breast higher than the fusing point of solid-state hindered phenol antioxidant 264
Change, obtain, through the solid-state age resistor of emulsifier, being added in toughness reinforcing latex through the solid-state age resistor of emulsifier, each group
Point mass fraction be：Toughness reinforcing latex（In terms of solid content）100th, solid-state hindered phenol antioxidant 264 3 ~ 5, emulsifying agent A 5 ~ 15,
Deionized water 20 ~ 50, wherein emulsifying agent A are dodecyl sodium sulfate.
3. method according to claim 2, it is characterised in that emulsification system temperature is 60 ~ 90 DEG C, the stirring speed of emulsification system
Spend is 100 ~ 400 minutes/turns.
4. method according to claim 1 and 2, it is characterised in that the toughness reinforcing latex is NBR latex.
5. method according to claim 4, it is characterised in that the toughness reinforcing latex is that acrylonitrile content is 30 ~ 40%, solid content
>=40%, the NBR latex of the degree of cross linking >=70%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610558837.7A CN106893159A (en) | 2016-07-17 | 2016-07-17 | A kind of preparation method of ageing whiteness toughening PVC resin high |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610558837.7A CN106893159A (en) | 2016-07-17 | 2016-07-17 | A kind of preparation method of ageing whiteness toughening PVC resin high |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106893159A true CN106893159A (en) | 2017-06-27 |
Family
ID=59191599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610558837.7A Pending CN106893159A (en) | 2016-07-17 | 2016-07-17 | A kind of preparation method of ageing whiteness toughening PVC resin high |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106893159A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921440A (en) * | 2009-06-16 | 2010-12-22 | 中国石油化工股份有限公司 | Method for improving ageing whiteness of toughening type PVC (Polyvinyl Chloride) resin |
-
2016
- 2016-07-17 CN CN201610558837.7A patent/CN106893159A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921440A (en) * | 2009-06-16 | 2010-12-22 | 中国石油化工股份有限公司 | Method for improving ageing whiteness of toughening type PVC (Polyvinyl Chloride) resin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9156920B2 (en) | Process for the preparation of an aqueous emulsifier-stabilized vinyl acetate-ethylene copolymer dispersion with fine particle size | |
| CN103980432B (en) | Containing polycarboxylate water-reducer and its preparation method of modified soluble acrylate | |
| KR101391048B1 (en) | MBS Graft Copolymer, Method For Preparing The Same And PVC Composition Containing The Same | |
| EP0188721A1 (en) | Inverse emulsion polymers with improved incorporation of diallyldimethylammonium chloride | |
| US3375238A (en) | Process for suspension polymerization of vinyl chloride | |
| KR20140118340A (en) | Impact reinforce agent for PVC, a method for preparing the same, and a resin composition containing the same | |
| KR950006125B1 (en) | Colloidal stable vinyl halide polymerization with mercaptan cain transfer agents | |
| CN101921440B (en) | Method for improving ageing whiteness of toughening type PVC (Polyvinyl Chloride) resin | |
| US2564291A (en) | Homopolymerization of vinyl chloride in aqueous medium with phenol-aldehyde condensation product as emulsifying agent | |
| CN106893159A (en) | A kind of preparation method of ageing whiteness toughening PVC resin high | |
| WO2008035929A1 (en) | Acrylic copolymer for processing aid of vinyl chloride resin composition, method for preparing the same and vinyl chloride resin composition containing the same | |
| CN103951790A (en) | Vinyl acetate emulsion and preparation process thereof | |
| CN107011589A (en) | A kind of method for improving polyvinyl chloride resin ageing whiteness | |
| CN107011588A (en) | A kind of method for improving polyvinyl chloride resin ageing whiteness | |
| US5290852A (en) | Glutaric acid based polyester internally plasticized PVC | |
| KR101620134B1 (en) | Graft copolymer using water-soluble comonomer and method of preparing the same and polyvinyl chloride resin composition comprising copolymer | |
| KR101508037B1 (en) | Method of preparing water-resistant vinylchloride resin | |
| JPS5817209B2 (en) | Netsukaso Seijyuushi no Seizouhou | |
| US8642698B2 (en) | Copolymerizable (meth)acrylic acid esters | |
| CN105273119B (en) | A kind of preparation method of high degree of polymerization of polyvinyl chloride resin | |
| KR101553099B1 (en) | Method of preparing vinyl chloride resin having excellent processibility and productivity | |
| KR101424879B1 (en) | Viscosity reducing agent for paste vinyl chloride resins and and method for controlling viscosity of paste vinyl chloride resin using thereof | |
| JP3469377B2 (en) | Method for producing vinyl chloride polymer | |
| JPH01256506A (en) | Alpha-methylstyrene and acrylonitrile copolymer and its production | |
| KR20110099968A (en) | A method for preparing vinyl chlorides resin having good polymerization productivity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170627 |