CN105482166A - Non-toxic environment-friendly stabilizer auxiliary agent and preparation method thereof - Google Patents
Non-toxic environment-friendly stabilizer auxiliary agent and preparation method thereof Download PDFInfo
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- CN105482166A CN105482166A CN201511030509.1A CN201511030509A CN105482166A CN 105482166 A CN105482166 A CN 105482166A CN 201511030509 A CN201511030509 A CN 201511030509A CN 105482166 A CN105482166 A CN 105482166A
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- auxiliary agent
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- asepsis environment
- stablizer
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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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
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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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
- C08K5/54—Silicon-containing compounds
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- 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 a stabilizer auxiliary agent, in particular to a non-toxic environment-friendly stabilizer auxiliary agent and a preparation method thereof. The stabilizer auxiliary agent is prepared from, by weight, 45-65 parts of calcium acetylacetonate, 30-40 parts of modified molecular sieves, 5-10 parts of a chelating agent and 5-10 parts of a coupling agent. A preparation method of the modified molecular sieves comprises the steps of conducting drying and dehydration treatment on molecular sieves, then mixing the molecular sieves with pentaerythritol ester and diisooctyl phenyl phosphite, and grinding the mixture, so that the modified molecular sieves are obtained. When the non-toxic environment-friendly stabilizer auxiliary agent is used, such constituents as beta-diketone, bisphenol A and pentaerythrite in a traditional calcium-zinc stabilizer formula can be substituted, the consumption of hard calcium and hard zinc is reduced, the excellent synergistic effect and lubricating effect are achieved, heat stability time of a PVC product can be prolonged, the precipitation and blooming phenomena are prevented, later-period weatherability is improved, and production cost is lowered. The invention further provides the preparation method of the non-toxic environment-friendly stabilizer auxiliary agent.
Description
Technical field
The present invention relates to a kind of stablizer auxiliary agent, be specifically related to a kind of asepsis environment-protecting stablizer auxiliary agent and preparation method thereof.
Background technology
Polyvinyl chloride (PVC) is one of a kind of the most frequently used plastics, and its advantage is that intensity is high, good insulating, price be lower than PP, PE.Its maximum shortcoming is under processing temperature condition or under being heated for a long time, easily decomposes, and terms of settlement adds thermo-stabilizer in the PVC course of processing, stops or delay this process.In addition, polyvinyl chloride be heated or by ultraviolet radiation time, also can cause polymer degradation and de-HCl.Stablizer is a kind of chemical assistant, can suppress PVC in machine-shaping and use procedure due to heat, light action and the degraded that causes and variable color.Stablizer can be divided into the large class of base lead salt stablizer, metal soap, organo-tin compound, organic stabilizer and one package stabilizer five by its chemical structure.
As everyone knows, traditional calcium zinc stabilizer is a kind of raw material mainly improving initial coloration with Zinic stearas, but Zinic stearas exists the processing later stage promotes the determination that PVC decomposes.Due in the course of processing, Zinic stearas unstable Cl in PVC is combined, form zinc chloride, it can accelerated degradation PVC, and it promotes that PVC degradation speed will promote the speed of degraded far away higher than HCl of PVC release, so must add stable component or sequestrant goes in conjunction with zinc chloride, but normal auxiliary stabilizer market value is higher, greatly can improve the cost value of calcium zinc stabilizer like this, equilibrium price and performance are a contradiction, become this object research emphasis.
In recent years, along with the enhancing of environmental consciousness and the constantly perfect of various law, the application of lead salt one package stabilizer is restricted, and the exploitation of enterprise to non-toxic, environmental friendly stablizer indicates strong interest.
The great advantage of asepsis environment-protecting stable composition agent aid is a kind of raw material that application medicine uses, and this type of material has certain initial stage stabilising effect, can improve the primary stability energy of PVC product, but addition is crossed conference and caused weather resistance poor.
Summary of the invention
For the deficiencies in the prior art, the object of this invention is to provide a kind of asepsis environment-protecting stablizer auxiliary agent, the composition such as beta-diketon, dihydroxyphenyl propane, tetramethylolmethane in use in alternative traditional calcium zinc stabilizer in formula, reduces the consumption of hard calcium hard zinc, can improve the thermostability time of PVC product, raising initial stage whiteness, avoid using Zinic stearas, reduce costs, prevent precipitation, bloom phenomenon, improve later stage weathering resistance, the present invention also provides its preparation method.
Asepsis environment-protecting stablizer auxiliary agent of the present invention, comprises the raw material of following parts by weight:
Wherein:
Modified molecular screen is: molecular sieve is carried out oven dry except water treatment, then mix with pentaerythritol ester and diisooctyl phenyl phosphite, grind, obtain modified molecular screen.
The mass ratio of diisooctyl phenyl phosphite and pentaerythritol ester is 1:1-1:1.5.
The mass ratio of the mixture of the molecular sieve after oven dry and diisooctyl phenyl phosphite and pentaerythritol ester is 15:4-15:5.
As the preferred technical scheme of one, modified molecular screen is: 4A type molecular sieve is placed in retort furnace and carries out oven dry except water treatment, temperature is 250 DEG C ~ 260 DEG C, then mix with pentaerythritol ester and diisooctyl phenyl phosphite and be placed in high-speed mixer and mix, be cooled to room temperature, abundant grinding, obtains modified molecular screen.
Wherein: the rotating speed of high-speed mixer is 800-1000r/min.
Mixing time is 10-12min.
Sequestrant is preferably beta-diketon.
Coupling agent is preferably silane coupling agent, commercially available prod.
The preparation method of asepsis environment-protecting stablizer auxiliary agent of the present invention, comprises the following steps:
In high-speed mixer, add calcium acetylacetonate be warmed up to 70-80 DEG C, add modified molecular screen and be incubated Keep agitation at 110-115 DEG C, add sequestrant and coupling agent, after stirring, release material and obtain product.
Wherein: the rotating speed of high-speed mixer is 800-1000r/min.
In sum, the present invention has the following advantages:
(1) asepsis environment-protecting stablizer auxiliary agent of the present invention, take calcium acetylacetonate as major stable component, by calcium acetylacetonate and modified molecular screen is composite forms, add sequestrant, coupling agent, the composition such as beta-diketon, dihydroxyphenyl propane, tetramethylolmethane in use in alternative traditional calcium zinc stabilizer in formula, reduce the consumption of hard calcium hard zinc, possess excellent synergistic effect and lubricating effect, the thermostability time of PVC product can be improved, prevent precipitation, bloom phenomenon, improve later stage weathering resistance, reduce production cost.
(2) test by GB GB2113-82 " plastics whiteness experimental technique ", the calcium zinc stabilizer that with the addition of stablizer auxiliary agent of the present invention, compared with traditional calcium zinc stabilizer, has outstanding initial stage whiteness, has good thermal stability.Carry out dynamic stability performance simultaneous test and find that the molecular sieve asepsis environment-protecting stablizer using the present invention to prepare can make the plasticizing capacity of PVC plastic strengthen, Dynamic Thermal obviously extends steady time.
(3) the present invention can improve initial stage retention of whiteness energy, avoids using Zinic stearas for improving the raw material of initial stage whiteness, greatly reduces the interpolation of the component such as inner complex and antioxygen, reduces traditional calcium zinc stabilizer formulation cost.
(4) the present invention's modified molecular screen improves the stability that PVC processes mid-term, and price is low, excellent performance.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1-3
The preparation of modified molecular screen:
Take 300g4A type molecular sieve to be placed in retort furnace and to carry out high temperature dehydration process, temperature is 255 ± 5 DEG C, keep 2 hours, take out the molecular sieve that thermal treatment is good, take 150g and diisooctyl phenyl phosphite 20g, pentaerythritol ester 20g, mix in high mixer, keep 5 minutes, grind after taking-up, sieve and obtain white powder modified molecular screen.
Being prepared as follows of novel molecular sieve asepsis environment-protecting stablizer auxiliary agent:
In high-speed mixer, add calcium acetylacetonate and be warmed up to 75 ± 5 DEG C, be incubated Keep agitation at continuing to add modified molecular screen 110 DEG C, add sequestrant, coupling agent, after stirring, release material, obtain product.
The formula of each raw material of embodiment 1 ~ 3 is in table 1.
The formula of each raw material of table 1 embodiment 1 ~ 3
In table 1, all numerical value units are parts by weight.
Use the novel molecular sieve asepsis environment-protecting stablizer auxiliary agent prepared by embodiment 1 ~ 3 to prepare PVC, technique adopts existing common process, and concrete formula and content are in table 2.
Table 2 uses the stablizer auxiliary agent prepared by embodiment 1 ~ 3 to prepare formula and the content of PVC.
In table 2, all numerical value units are parts by weight, and "/" represents does not add.
PVC prepared by the stablizer auxiliary agent prepared by above-mentioned interpolation embodiment 1 ~ 3 and the PVC (comparative example 1) adopting traditional calcium zinc stabilizer to prepare carry out heat-resisting whiteness experiment.Test piece being placed on by whiteness is that the relative whiteness value tested in the verified whiteness instrument of standard white body of 85% is in table 3.Can find from table 3, embodiment 1-3, compared with comparative example, has outstanding thermostability.
The heat-resisting whiteness experiment of table 3
In table except digestion time, its remainder values unit is relative whiteness %.
Rheology testing the results are shown in Table 4.
Table 4 rheology testing result
By dynamic thermal stability energy contrast experiment, the thermal decomposition time namely in table 4, can find that the molecular formula asepsis environment-protecting stablizer auxiliary agent using the present invention to prepare can make the dynamic thermal stability time of PVC plastic rise appreciably.
Claims (10)
1. an asepsis environment-protecting stablizer auxiliary agent, is characterized in that: the raw material comprising following parts by weight:
2. asepsis environment-protecting stablizer auxiliary agent according to claim 1, is characterized in that: modified molecular screen is: molecular sieve is carried out oven dry except water treatment, then mix with pentaerythritol ester and diisooctyl phenyl phosphite, grind, obtain modified molecular screen.
3. asepsis environment-protecting stablizer auxiliary agent according to claim 2, is characterized in that: the mass ratio of diisooctyl phenyl phosphite and pentaerythritol ester is 1:1-1:1.5.
4. asepsis environment-protecting stablizer auxiliary agent according to claim 2, is characterized in that: the mass ratio of the mixture of the molecular sieve after oven dry and diisooctyl phenyl phosphite and pentaerythritol ester is 15:4-15:5.
5. asepsis environment-protecting stablizer auxiliary agent according to claim 2, it is characterized in that: modified molecular screen is: 4A type molecular sieve is placed in retort furnace and carries out oven dry except water treatment, temperature is 250 DEG C ~ 260 DEG C, then mix with pentaerythritol ester and diisooctyl phenyl phosphite and be placed in high-speed mixer and mix, be cooled to room temperature, abundant grinding, obtains modified molecular screen.
6. asepsis environment-protecting stablizer auxiliary agent according to claim 5, is characterized in that: the rotating speed of high-speed mixer is 800-1000r/min; Mixing time is 10-12min.
7. asepsis environment-protecting stablizer auxiliary agent according to claim 1, is characterized in that: sequestrant is beta-diketon.
8. asepsis environment-protecting stablizer auxiliary agent according to claim 1, is characterized in that: coupling agent is silane coupling agent.
9. a preparation method for the arbitrary described asepsis environment-protecting stablizer auxiliary agent of claim 1-8, is characterized in that: comprise the following steps:
In high-speed mixer, add calcium acetylacetonate be warmed up to 70-80 DEG C, add modified molecular screen and be incubated Keep agitation at 110-115 DEG C, add sequestrant and coupling agent, after stirring, release material and obtain product.
10. the preparation method of asepsis environment-protecting stablizer auxiliary agent according to claim 9, is characterized in that: the rotating speed of high-speed mixer is 800-1000r/min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511030509.1A CN105482166B (en) | 2015-12-31 | 2015-12-31 | Asepsis environment-protecting stablizes agent aid and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201511030509.1A CN105482166B (en) | 2015-12-31 | 2015-12-31 | Asepsis environment-protecting stablizes agent aid and preparation method thereof |
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| CN105482166A true CN105482166A (en) | 2016-04-13 |
| CN105482166B CN105482166B (en) | 2018-05-25 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107936300A (en) * | 2017-12-20 | 2018-04-20 | 山东慧科助剂股份有限公司 | Perchlorate modified molecular screen stabilizer and preparation method thereof |
| CN108467553A (en) * | 2018-03-20 | 2018-08-31 | 山东三义实业股份有限公司 | Environmentally friendly calcium-zinc composite stabilizing agent for the processing of the floors WPC |
| CN109867882A (en) * | 2019-03-05 | 2019-06-11 | 河源市鑫达科技有限公司 | It is a kind of based on the PVC plastic of modified molecular screen heat stabilizer preparation process |
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| CN102585394A (en) * | 2011-12-05 | 2012-07-18 | 山东慧科助剂股份有限公司 | Calcium-zinc molecular sieve composite stabilizer for chloroethylene and preparation method thereof |
| CN102964744A (en) * | 2012-12-10 | 2013-03-13 | 山东慧科助剂股份有限公司 | Thermal stabilizer for aluminate modified molecular sieve PVC and preparation method thereof |
| CN103086857A (en) * | 2013-01-11 | 2013-05-08 | 浙江传化华洋化工有限公司 | Preparation method for high-brightness calcium acetylacetonate for PVC (Polyvinyl Chloride) heat stabilizer |
-
2015
- 2015-12-31 CN CN201511030509.1A patent/CN105482166B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585394A (en) * | 2011-12-05 | 2012-07-18 | 山东慧科助剂股份有限公司 | Calcium-zinc molecular sieve composite stabilizer for chloroethylene and preparation method thereof |
| CN102964744A (en) * | 2012-12-10 | 2013-03-13 | 山东慧科助剂股份有限公司 | Thermal stabilizer for aluminate modified molecular sieve PVC and preparation method thereof |
| CN103086857A (en) * | 2013-01-11 | 2013-05-08 | 浙江传化华洋化工有限公司 | Preparation method for high-brightness calcium acetylacetonate for PVC (Polyvinyl Chloride) heat stabilizer |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107936300A (en) * | 2017-12-20 | 2018-04-20 | 山东慧科助剂股份有限公司 | Perchlorate modified molecular screen stabilizer and preparation method thereof |
| CN108467553A (en) * | 2018-03-20 | 2018-08-31 | 山东三义实业股份有限公司 | Environmentally friendly calcium-zinc composite stabilizing agent for the processing of the floors WPC |
| CN109867882A (en) * | 2019-03-05 | 2019-06-11 | 河源市鑫达科技有限公司 | It is a kind of based on the PVC plastic of modified molecular screen heat stabilizer preparation process |
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| CN105482166B (en) | 2018-05-25 |
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Effective date of registration: 20211018 Address after: 256100 east section of Jingshan Road, Yiyuan County, Zibo City, Shandong Province Patentee after: Shandong Helong New Material Technology Co.,Ltd. Address before: 256100 Yiyuan Economic Development Zone, Zibo City, Shandong Province Patentee before: SHANDONG HUIKE ADDITIVES Co.,Ltd. |
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