CN106046618A - Application of bipyridine ester phosphite to PVC heat stabilizer - Google Patents
Application of bipyridine ester phosphite to PVC heat stabilizer Download PDFInfo
- Publication number
- CN106046618A CN106046618A CN201610547116.6A CN201610547116A CN106046618A CN 106046618 A CN106046618 A CN 106046618A CN 201610547116 A CN201610547116 A CN 201610547116A CN 106046618 A CN106046618 A CN 106046618A
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- Prior art keywords
- zinc
- stabilizer
- barium
- liquid
- ester
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- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5393—Phosphonous compounds, e.g. R—P(OR')2
-
- 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
-
- 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
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
-
- 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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- 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
Abstract
The invention relates to the application of bipyridine ester phosphite to a PVC heat stabilizer. bipyridine ester phosphite can be applied to preparation of a liquid barium-zinc stabilizer, a liquid barium-cadmium-zinc stabilizer and a liquid calcium-zinc stabilizer. The liquid barium-zinc stabilizer is prepared from, by weight, 40-50 parts of barium isotanoate, 10-15 parts of zinc-based complex, 5-10 parts of bipyridine ester phosphite, 2-7 parts of 2-ethyl acetyl benzoyl methane, 1-10 parts of thiodipropionicacid dilauryl ester and 10-20 parts of tripropylene glycol n-butyl ether. The bipyridine ester phosphite compound has a higher anti-precipitation property than aliphatic or aromatic phosphite ester by means of a novel heterocyclic perssad replacing the aliphatic or aromatic perssad during preparation of the liquid barium-zinc stabilizer, the liquid barium-cadmium-zinc stabilizer and the liquid calcium-zinc stabilizer. By introducing nitrogen atoms to the heterocyclic ring, the auxiliary stabilization effect on phosphite ester is improved remarkably, and then the printing performance and stability of a modified PVC product are improved.
Description
Technical field
The present invention relates to the application in PVC heat stabilizer of a kind of phosphorous acid two pyridine ester.
Background technology
Polrvinyl chloride (PVC) is the second largest plastics variety being only second to polyethylene, has higher intensity and excellent resistance to
Corrosivity and insulating properties, its goods are widely used in the industries such as building, electrical equipment, toy, packaging.But PVC has its fault of construction,
Instability during heating, decomposes and discharges hydrogen chloride gas, and solution is to add heat stabilizer in PVC processes.Liquid is multiple
Close stabilizer to produce and application process no dust pollution because of it, it is simple to metering and the advantage such as cheap, in flexible PVC goods
Obtain increasingly being widely applied.
Traditional liquid stabilisers is bad due to the compatibility of metallic soap and polyvinyl chloride resin, during PVC calendering formation
Constantly precipitating metal soap, precipitate is attached to the surface of PVC film, affects the printing of goods, air brushing and the transparency；Secondly, at present
Liquid composite thermal stabilizer mainly uses fatty acid calcium salt and fatty acid zinc salt to be main stabilizer, and fatty acid calcium salt has serious
Plate-out, fatty acid zinc has serious bloom phenomenon, therefore causes existing liquid composite stabilizing agent product to there is significantly pressure
The problems such as analysis and bloom.This all uses aliphatic or aromatic series phosphorous acid as anti-mainly due to traditional liquid stabilisers
Precipitation agent, its anti-precipitation performance and supplemental stability can not be good, ultimately limit liquid stabilisers extensively should in PVC field
With.
Summary of the invention
It is an object of the invention to solve the deficiencies in the prior art, it is provided that a kind of phosphorous acid two pyridine ester is thermally-stabilised at PVC
Application in agent.This phosphorous acid two pyridine ester adds in PVC liquid stabilisers, can be obviously improved PVC soft goods flattener
Precipitation in skill, significantly improves printing and the stability of goods.
The technical solution adopted for the present invention to solve the technical problems is:
The application in PVC heat stabilizer of a kind of phosphorous acid two pyridine ester, described phosphorous acid two pyridine ester is preparing liquid
Application in barium zinc stabilizer, liquid barium cadmium zinc stabilizer and liquid calcium zinc stabilizer.
The structural formula of phosphorous acid two pyridine ester is as follows:
Pyridine therein is 2 hydroxy pyrimidine and/or 3-pyridone.This phosphorous acid two pyridine ester compound is with novel
Heterocyclic group replaces aliphatic and aromatic group, is preparing liquid barium zinc stabilizer, liquid barium cadmium zinc stabilizer and liquid calcium
Application in zinc stabilizer embodies the anti-precipitation more more excellent than aliphatic and aromatic series phosphite ester, heterocycle introduces nitrogen
Atom, is also obviously improved the auxiliary Stabilization of phosphite ester, thus the printing performance of modified PVC goods and stability
Energy.
Preferably, described liquid barium zinc stabilizer is formed by the Raw material processing of following weight portion:
Described zinc-base coordination compound is that zinc acetylacetonate, zinc glycinate, p-tert-butyl benzoic acid zinc and TGA are against thioesters
The compositions of zinc.
Preferably, described liquid barium zinc stabilizer is formed by the Raw material processing of following weight portion:
It is furthermore preferred that the weight portion of described zinc-base coordination compound consists of: zinc acetylacetonate 30-45 part, zinc glycinate 5-15
Part, p-tert-butyl benzoic acid zinc 3-10 part, TGA is against thioesters zinc 2-8 part.
Preferably, the preparation method of described liquid barium zinc stabilizer is carried out as follows:
(1) isooctyl acid barium, zinc-base coordination compound and tripropylene glycol butyl ether are mixed in proportion, be heated to while stirring
75-80℃；
(2) in step (1), add phosphorous acid two pyridine ester, be heated to 85-90 DEG C, add the double dodecane of thio-2 acid
Ester mixes；
(3) in step (2), add 2-ethyl acyl benzoyl methane, be incubated 30-45min in 85-90 DEG C, then through cold
But, filter, obtain liquid zinc barium stabilizer.
The invention has the beneficial effects as follows:
(1) phosphorous acid two pyridine ester compound replaces aliphatic and aromatic group with novel heterocyclic group, in preparation
Application in liquid barium zinc stabilizer, liquid barium cadmium zinc stabilizer and liquid calcium zinc stabilizer embodies than aliphatic and fragrance
The anti-precipitation that race's phosphite ester is more excellent, introduces nitrogen-atoms, also has the auxiliary Stabilization of phosphite ester significantly in heterocycle
Promote, thus the printing performance of modified PVC goods and stability.
(2) the liquid barium zinc stabilizer containing phosphorous acid two pyridine ester of the present invention, with multiple non-fat race zinc-based compounds
Compound as main stabilizer with isooctyl acid barium, substantially improve the initial coloring of PVC product, hence it is evident that reduce aliphatic zinc salt
Bloom problem, adds tripropylene glycol butyl ether, can improve the homogeneity of each component mixing in stabilizer, keep the steady of product quality
Qualitative.The liquid barium zinc stabilizer being processed into by the processing technique of the present invention, synergism between each component, reach good at the beginning of
Phase and long-time stability, printing performance and the stability of PVC product be substantially improved, PVC processing characteristics and good mechanical performance,
PVC product initial stage whiteness is good, no blooming.
Detailed description of the invention
Below by specific embodiment, technical scheme is described in further detail.
Raw materials used in embodiment is all commercial convenient source.
The preparation of phosphorous acid two pyridine:
With Phosphorous chloride. 68.5g, 2 hydroxy pyrimidine 150g as raw material, 2 hydroxy pyrimidine drips Phosphorous chloride., dropping
Temperature 65 DEG C, time for adding is 100 minutes, obtains tricresyl phosphite pyridone ester, puts into 20.5g phosphorous in above product
Acid, reacts 60 minutes under the conditions of 120 DEG C, obtains phosphorous acid dihydroxy-pyridine ester 98.5g.
The formula of the liquid barium zinc stabilizer of embodiment 1-4 forms such as following table:
In embodiment 1-4, the composition of zinc-base coordination compound is as follows, following raw materials is mixed by proportioning, then weighs liquid barium
Consumption in the formula of zinc stabilizer.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Zinc acetylacetonate | 30 | 45 | 35 | 40 |
| Zinc glycinate | 15 | 5 | 10 | 8 |
| P-tert-butyl benzoic acid zinc | 10 | 3 | 8 | 6 |
| TGA is against thioesters zinc | 2 | 8 | 5 | 6 |
The preparation method of the liquid barium zinc stabilizer of embodiment 1-4 is carried out as follows:
(1) isooctyl acid barium, zinc-base coordination compound and tripropylene glycol butyl ether are mixed in proportion, be heated to while stirring
75-80℃；
(2) in step (1), add phosphorous acid two pyridine ester, be heated to 85-90 DEG C, add the double dodecane of thio-2 acid
Ester mixes；
(3) in step (2), add 2-ethyl acyl benzoyl methane, be incubated 30-45min in 85-90 DEG C, then through cold
But, filter, obtain liquid zinc barium stabilizer.
One, precipitation property experiment
Experimental formula:
(a) basic components
Checking example 1-4:PVC (SG-1000, Qilu Co., Ltd., China Petrochemical Corp): 100g, embodiment 1-4 is prepared into
The liquid zinc barium stabilizer arrived: 2g, DOP (Qilu Co., Ltd., China Petrochemical Corp): 35g, red: 1g
(b) white material formula
PVC (SG-1000, Qilu Co., Ltd., China Petrochemical Corp): 100g, Methyltin composite heat stabilizer (Zhe Jianghai
Pu Dun new material limited company): 1g, DOP (Qilu Co., Ltd., China Petrochemical Corp): 45g, stearic acid (Huzhou City Pedicellus et Pericarpium Trapae
Hu Xinwang Chemical Co., Ltd.): 0.5g, titanium dioxide (E.I.Du Pont Company): 7g
(2) prepared by sample:
According to above-mentioned flexible PVC formula, the most accurately weigh material, mix homogeneously, at 180 ± 2 DEG C, join according to basis
Just go up mixing 10 minutes at opening rubber mixing machine (Hong Yang group), material is taken off, white material is added on unwashed roller, mixing
5 minutes, material being taken off, mixing about 5min, make the PVC coupons of thickness about 1mm, detect Da value, observe precipitation property, result is such as
Under:
| Embodiment | Checking example 1 | Checking example 2 | Checking example 3 | Checking example 4 |
| Da value | 0.5 | 0.3 | 0 | 0 |
Two, stability experiment
(1) flexible PVC formula:
Checking example 1-4:PVC (SG-1000, Qilu Co., Ltd., China Petrochemical Corp): 100g, embodiment 1-4 is prepared into
The liquid zinc barium stabilizer arrived: 2g, DOP (Qilu Co., Ltd., China Petrochemical Corp): 35g
(2) prepared by sample:
According to flexible PVC formula, by material mix homogeneously, under the conditions of 180 ± 2 DEG C, at opening rubber mixing machine (Hong Yangji
Group) upper mixing about 3min, makes the PVC coupons of thickness about 1mm.
(3) by the following method test PVC coupons thermal stability:
Prepared PVC coupons is cut into the sheet specimens of 1cm × 3cm, puts into full-automatic accurately test oven, place
Within 60 minutes, take sheet.
Static heat stabilization time: the time of PVC coupons blackening, baking the affected part after applying some drugs temperature is 195 ± 2 DEG C.Concrete method of testing is pressed
GB2410-80 is carried out, and result is as follows:
| Checking example | Static heat stabilization time |
| Checking example 1 | 65min |
| Checking example 2 | 62min |
| Checking example 3 | 68min |
| Checking example 4 | 66min |
Shown by precipitation property and stability test result: the liquid zinc barium stabilizer containing phosphorous acid two pyridine ester is used for PVC
The processing of goods, has anti-precipitation and the heat stability of excellence.
Embodiment described above is the one preferably scheme of the present invention, not makees the present invention any pro forma
Limit, on the premise of without departing from the technical scheme described in claim, also have other variant and remodeling.
Claims (5)
1. phosphorous acid two pyridine ester application in PVC heat stabilizer, it is characterised in that: phosphorous acid two pyridine ester is in preparation
Application in liquid barium zinc stabilizer, liquid barium cadmium zinc stabilizer and liquid calcium zinc stabilizer.
Phosphorous acid two pyridine ester application in PVC heat stabilizer the most according to claim 1, it is characterised in that: described liquid
Body barium zinc stabilizer is formed by the Raw material processing of following weight portion:
Described zinc-base coordination compound is that zinc acetylacetonate, zinc glycinate, p-tert-butyl benzoic acid zinc and TGA are against thioesters zinc
Compositions.
PVC heat stabilizer containing phosphorous acid two pyridine ester the most according to claim 2, it is characterised in that: described liquid
Barium zinc stabilizer is formed by the Raw material processing of following weight portion:
4. according to the PVC heat stabilizer containing phosphorous acid two pyridine ester described in Claims 2 or 3, it is characterised in that: described zinc
The weight portion of basigamy compound consists of: zinc acetylacetonate 30-45 part, zinc glycinate 5-15 part, p-tert-butyl benzoic acid zinc 3-10
Part, TGA is against thioesters zinc 2-8 part.
Phosphorous acid two pyridine ester application in PVC heat stabilizer the most according to claim 2, it is characterised in that: described liquid
The preparation method of body barium zinc stabilizer is carried out as follows:
(1) isooctyl acid barium, zinc-base coordination compound and tripropylene glycol butyl ether are mixed in proportion, be heated to 75-80 while stirring
℃；
(2) in step (1), add phosphorous acid two pyridine ester, be heated to 85-90 DEG C, add the double dodecane ester of thio-2 acid and mix
Even；
(3) add 2-ethyl acyl benzoyl methane in the step (2), be incubated 30-45min in 85-90 DEG C, the most cooled,
Filter, obtain liquid zinc barium stabilizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610547116.6A CN106046618B (en) | 2016-07-08 | 2016-07-08 | A kind of application of two pyridine ester of phosphorous acid in PVC heat stabilizer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610547116.6A CN106046618B (en) | 2016-07-08 | 2016-07-08 | A kind of application of two pyridine ester of phosphorous acid in PVC heat stabilizer |
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| Publication Number | Publication Date |
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| CN106046618A true CN106046618A (en) | 2016-10-26 |
| CN106046618B CN106046618B (en) | 2018-06-26 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107722614A (en) * | 2017-10-26 | 2018-02-23 | 湖北雄志塑胶五金制品有限公司 | A kind of composite resin material and preparation method thereof |
| CN112110956A (en) * | 2020-08-27 | 2020-12-22 | 赵东源 | Synthesis method of tris- (3,5, 6-trichloropyridine) phosphite |
| CN113831593A (en) * | 2021-10-22 | 2021-12-24 | 浙江海普顿新材料股份有限公司 | Application of biquinoline phosphite ester in PVC barium-zinc composite heat stabilizer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219926A (en) * | 2011-04-18 | 2011-10-19 | 浙江海普顿化工科技有限公司 | Zinc base liquid composite heat stabilizer and preparation method of zinc base liquid composite heat stabilizer |
| CN103980537A (en) * | 2014-06-03 | 2014-08-13 | 江苏联盟化学有限公司 | Novel liquid stabilizer compounded with acid phosphite ester and preparation process of novel liquid stabilizer |
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2016
- 2016-07-08 CN CN201610547116.6A patent/CN106046618B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219926A (en) * | 2011-04-18 | 2011-10-19 | 浙江海普顿化工科技有限公司 | Zinc base liquid composite heat stabilizer and preparation method of zinc base liquid composite heat stabilizer |
| CN103980537A (en) * | 2014-06-03 | 2014-08-13 | 江苏联盟化学有限公司 | Novel liquid stabilizer compounded with acid phosphite ester and preparation process of novel liquid stabilizer |
Non-Patent Citations (1)
| Title |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107722614A (en) * | 2017-10-26 | 2018-02-23 | 湖北雄志塑胶五金制品有限公司 | A kind of composite resin material and preparation method thereof |
| CN107722614B (en) * | 2017-10-26 | 2020-07-17 | 湖北雄志塑胶五金制品有限公司 | Composite resin material and preparation method thereof |
| CN112110956A (en) * | 2020-08-27 | 2020-12-22 | 赵东源 | Synthesis method of tris- (3,5, 6-trichloropyridine) phosphite |
| CN112110956B (en) * | 2020-08-27 | 2022-08-09 | 赵东源 | Synthesis method of tris- (3,5, 6-trichloropyridine) phosphite |
| CN113831593A (en) * | 2021-10-22 | 2021-12-24 | 浙江海普顿新材料股份有限公司 | Application of biquinoline phosphite ester in PVC barium-zinc composite heat stabilizer |
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| CN106046618B (en) | 2018-06-26 |
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