CN106243462A - Calcium zinc stabilizer and preparation method thereof - Google Patents
Calcium zinc stabilizer and preparation method thereof Download PDFInfo
- Publication number
- CN106243462A CN106243462A CN201610756484.1A CN201610756484A CN106243462A CN 106243462 A CN106243462 A CN 106243462A CN 201610756484 A CN201610756484 A CN 201610756484A CN 106243462 A CN106243462 A CN 106243462A
- Authority
- CN
- China
- Prior art keywords
- stabilizer
- calcium
- zinc
- calcium zinc
- stearate
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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)
Abstract
The invention discloses a kind of calcium zinc stabilizer and preparation method thereof, this calcium zinc stabilizer is made up of the raw material of following mass percent: calcium stearate 10% 12%, zinc stearate 4% 5%, beta diketone 8% 10%, phosphite ester 4% 30%, antioxidant 12% 15%, brucite 9% 16%, PE wax 13% 19%, epoxidized linseed oil 4% 10%, auxiliary stabilizer 1% 3%.The present invention is nontoxic product, meet national requirements for environmental protection, can effectively suppress PVC material being heated when processing and forming, rub, the physical action such as shearing and the external condition such as light, thermal oxide causes during using degraded, it is to avoid PVC product rough surface, alveolate problem.
Description
Technical field
The present invention relates to a kind of stabilizer and preparation method thereof, particularly relate to a kind of calcium zinc stabilizer and preparation side thereof
Method.
Background technology
Along with the enhancing of countries in the world environmental consciousness, environmental regulation is the most perfect, particularly medicine, food processing, daily
The plastic hygienic requirements such as product, plastic toys improves, and lead, cadmium salt class stabilizer are the most comprehensively by nontoxic PVC stabilizer institute
Replace.External plastic additive produces and will develop to the large-scale customizations that becomes, environmental requirement attention, high efficiency and multi-function direction, research
Nontoxic PVC stabilizer friendly with exploitation novel environmental has become inexorable trend.The Non-toxic direction of PVC heat stabilizer is mainly concentrated
At organotin and Ca-Zn composite heat stabilizer two aspect, and all make significant progress.It is mainly manifested in the U.S. is representative
Organo-tin het stabilizer is studied successfully and a large amount of use, and the popularization of the nontoxic calcium zinc composite thermal stabilizer with Europe as representative should
With, but the expensive of organotin.The nontoxic PVC stabilizer body that calcium-zinc composite stabilizing agent is following by finally building countries in the world
System.And China still accounts for main flow with one-component powdery lead salt and metallic soap salt, compared with abroad, kind and performance and market demands phase
Difference is very remote, though liquid composite stabilizing agent yield has some to increase, but proportion is little, therefore, and grinding of environmental friendliness new varieties
Study carefully and also do not have great breakthrough with exploitation.
Ca-Zn composite heat stabilizer is roughly divided into two classes at present: solid calcium Zn composite heat stabilizer, liquid Ca Zn composite are steady
Determine agent.Solid calcium Zn composite heat stabilizer is the product at Ca-Zn composite heat stabilizer class initial stage, but its development is also far from reaching
To full ripe stage.Liquid calcium zinc complex stabilizer is being applied in PVC processing of a kind of nontoxic, transparent, low cost
New Heat Stabilizer, but when using, easily there is the time that zinc burns.
The product of non-lead class series is presently the most widely used that organotin series.But high price limit it
Bigger growth is had in quantity.Calcium-zinc composite stabilizing agent, due to avirulent advantage, is often proposed to replace lead salt, but only limits
Production for flexible PVC goods.
Polrvinyl chloride (PVC) is one of general five big synthetic resin, because it has excellent combination property, is widely used in
The every field such as industrial building, agricultural, article of everyday use, public utilities, current production rate is only second to polyethylene (PE), occupies in the plastic
2.Owing to PVC processing heat stability is poor, must be added to heat stabilizer when its processing and forming, common heat stabilizer mainly has
The stabilizers such as lead salts, metal soap, organic tin, terres rares and Ca/Zn class.From the nineties in 20th century, the most especially
It is that western countries forbid that in heat stabilizer, the cry of the heavy metal such as leaded cadmium grows to even greater heights.On January 27th, 2003, European Union is the most formal
Disclose " scrapping electronic and electrical equipment instruction " (WEEE) and " about prohibitting the use of some harmful substance in electronic electric equipment
Instruction " (RoHs).Command request, from 1 day July in 2006, is forbidden selling containing lead, hydrargyrum, cadmium, Cr VI, many at EU market
Bromo biphenyl and the electronic electric equipment of 6 kinds of harmful substances of PBDEs；In May, 2006, ESPA and EUPC joint commitments European Union
To completely forbid in 2015 and use leaded PVC stabilizer, and European Union Vinyl2010 will also prohibit containing cadmium stable at the end of 2006
The use of agent.Therefore, the most worldwide, nontoxic, pollution-free, compound and efficient to have become PVC heat stabilizer irreversible
The development trend turned.And nontoxic Ca/Zn heat stabilizer is nontoxic, the environment-benign heat stabilizer generally acknowledged the most in the world, and have
The advantages such as cheap, lubricity is good, therefore have the most wide development space.
In polrvinyl chloride and vinyl chloride copolymer are processed, it is necessary to using heat stabilizer, it can prevent PVC in the course of processing
In degraded caused by heat and mechanical shearing, prevent the destruction of goods in use heat, light, oxygen.Thermally-stabilised
Agent is mainly by lead salts, organic metal soaps, organic tin, complex stabilizer class, organic heat stabilizers class etc..Wherein, lead salt,
Barium cadmium soaps heat stabilizer because of cheap and function admirable, its yield of developed country account for heat stabilizer total amount 60%～
70%；Bigger in China's ratio, account for 80%～90%.For a long time, lead, cadmium stabilizer dominate world PVC heat surely always
Determine the consumption market of agent.But owing to lead salt and barium cadmium soaps heat stabilizer toxicity are big, health there is is serious threat.20th century
Since the seventies, World Developed Countries, the state such as particularly American-European has been fully recognized that environmental problem that lead, cadmium etc. cause is day by day
Seriously, the restriction the strictest to the use of lead, cadmium salt, the particularly safety such as packaging for foodstuff, medical sanitary apparatus is asked
Topic causes people to pay much attention to, and countries in the world research and develop lead, cadmium succedaneum one after another.There is heat stabilizer manufacturer more than 90 in China
Family, heat stabilizer yield 50,000 about t, the not perfectly flat weighing apparatus of product structure, lead, cadmium series products account for thumping majority, and nontoxic variety yield
Less than 15%.After accession to WTO, environmental consciousness is further enhanced by people, and friendly nontoxic PVC is stable for research and development novel environmental
Agent has become inexorable trend.
Summary of the invention
The technical problem to be solved is to provide a kind of calcium zinc stabilizer and preparation method thereof, and it is nontoxic
Product, meets national requirements for environmental protection, can effectively suppress PVC material being heated when processing and forming, rub, the physical action such as shearing
The degraded caused with the external condition such as light, thermal oxide during use, it is to avoid PVC product rough surface, alveolate problem.
The present invention solves above-mentioned technical problem by following technical proposals: a kind of calcium zinc stabilizer, its feature exists
In, it is made up of the raw material of following mass percent: calcium stearate 10%-12%, zinc stearate 4%-5%, beta-diketon 8%-
10%, phosphite ester 4%-30%, antioxidant 12%-15%, brucite 9%-16%, PE wax 13%-19%, epoxidized linseed oil
4%-10%, auxiliary stabilizer 1%-3%.
Preferably, described antioxidant be four [β-(3,5-di-t-butyl 4-hydroxy phenyl) propanoic acid] pentaerythritol esters or β-
(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester.
Preferably, described brucite is organic hydrotalcite or zinc-magnesium-aluminium ternary hydrotalcite.
Preferably, described auxiliary stabilizer is tetramethylolmethane or dipentaerythritol or polyvinyl alcohol or Bis(pentaerythritol).
The present invention also provides for the preparation method of a kind of calcium zinc stabilizer, it is characterised in that comprise the following steps:
Step one, by calcium stearate 10%-12%, zinc stearate 4%-5%, beta-diketon 8%-10%, phosphite ester
4%-30%, antioxidant 12%-15%, brucite 9%-16%, PE wax 13%-19%, epoxidized linseed oil 4%-10%, auxiliary
Stabilizer 1%-3% carries out being mixed to form compound in a blending bin；
Step 2, compound is stirred in blender；
Step 3, the compound after stirring heats in a reactor, and heat time heating time is ten minutes to 30 points
Clock, obtains product of the present invention after cooling.
The most progressive effect of the present invention is: calcium zinc stabilizer of the present invention is nontoxic product, meets national environmental protection
Requirement, can effectively suppress PVC material being heated when processing and forming, rub, the physical action such as shearing and light during using,
The degraded that the external conditions such as thermal oxide cause, improves thermal stability and the efficiency of stabilizer, it is to avoid PVC product rough surface,
Alveolate problem, low cost, it is simple to manufacture and convenient.
Accompanying drawing explanation
Fig. 1 is the flow chart of the preparation method of calcium zinc stabilizer of the present invention.
Detailed description of the invention
Provide present pre-ferred embodiments below in conjunction with the accompanying drawings, to describe technical scheme in detail.
Calcium zinc stabilizer of the present invention is made up of the raw material of following mass percent: calcium stearate 10%-12%, zinc stearate
4%-5%, beta-diketon 8%-10%, phosphite ester 4%-30%, antioxidant 12%-15%, brucite 9%-16%, PE wax
13%-19%, epoxidized linseed oil 4%-10%, auxiliary stabilizer 1%-3%.
Antioxidant is four [β-(3,5-di-t-butyl 4-hydroxy phenyl) propanoic acid] pentaerythritol ester or β-(3,5-bis-tertiary fourths
Base-4-hydroxy phenyl) propanoic acid positive octadecanol ester, such low cost, antioxidant effect is good.
Brucite is organic hydrotalcite or zinc-magnesium-aluminium ternary hydrotalcite, such low cost.
Auxiliary stabilizer is tetramethylolmethane or dipentaerythritol or polyvinyl alcohol or Bis(pentaerythritol), such low cost, increases
Add stability.
As it is shown in figure 1, the preparation method of calcium zinc stabilizer of the present invention comprises the following steps:
Step one, by calcium stearate 10%-12%, zinc stearate 4%-5%, beta-diketon 8%-10%, phosphite ester
4%-30%, antioxidant 12%-15%, brucite 9%-16%, PE wax 13%-19%, epoxidized linseed oil 4%-10%, auxiliary
Stabilizer 1%-3% carries out being mixed to form compound in a blending bin；
Step 2, compound is stirred in blender；
Step 3, the compound after stirring heats in a reactor, and heat time heating time is ten minutes to 30 points
Clock, obtains product of the present invention after cooling.
Embodiment 1
By calcium stearate 12%, zinc stearate 5%, beta-diketon 8%, phosphite ester 4%, antioxidant 15%, brucite
16%, PE wax 19%, epoxidized linseed oil 10%, auxiliary stabilizer 1% carry out being mixed to form compound in a blending bin；Mixed
Close material to be stirred in blender；Compound after stirring heats in a reactor, and heat time heating time is ten minutes,
Product of the present invention is obtained after cooling.
Embodiment 2
By calcium stearate 10%, zinc stearate 4%, beta-diketon 10%, phosphite ester 24%, antioxidant 12%, brucite
11%, PE wax 18%, epoxidized linseed oil 9%, auxiliary stabilizer 2% carry out being mixed to form compound in a blending bin；Mixed
Close material to be stirred in blender；Compound after stirring heats in a reactor, and heat time heating time is 30 points
Clock, obtains product of the present invention after cooling.
Embodiment 3
By calcium stearate 11%, zinc stearate 4.5%, beta-diketon 9.5%, phosphite ester 30%, antioxidant 13%, neatly
Stone 13%, PE wax 13%, epoxidized linseed oil 4%, auxiliary stabilizer 3% carry out being mixed to form compound in a blending bin；
Compound is stirred in blender；Compound after stirring heats in a reactor, and heat time heating time is 20
Minute, obtain product of the present invention after cooling.
Calcium zinc stabilizer of the present invention is nontoxic product, meets national requirements for environmental protection, can effectively suppress PVC material becoming
Type add being heated of man-hour, rub, the physical action such as shearing and the external condition such as light, thermal oxide causes during using fall
Solve, it is to avoid PVC product rough surface, alveolate problem, low cost, be simple to manufacture and convenient, improve the thermally-stabilised of stabilizer
Performance and efficiency, promoted the development of PVC machine-shaping industry greatly, it is possible to produces the PVC product of more high-quality, right
The development of PVC industry has induced effect.Introducing has the auxiliary stabilizer of cooperative effect can improve the heat of calcium zinc stabilizer surely
Determine efficiency, i.e. develop efficient auxiliary stabilizer, thus improve the initial coloring of PVC and improve the long-term thermal stability of PVC.
Particular embodiments described above, solves the technical problem that the present invention, technical scheme and beneficial effect are carried out
Further describe, be it should be understood that the specific embodiment that the foregoing is only the present invention, be not limited to
The present invention, all within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. done, should be included in this
Within the protection domain of invention.
Claims (5)
1. a calcium zinc stabilizer, it is characterised in that it is made up of the raw material of following mass percent: calcium stearate 10%-
12%, zinc stearate 4%-5%, beta-diketon 8%-10%, phosphite ester 4%-30%, antioxidant 12%-15%, brucite
9%-16%, PE wax 13%-19%, epoxidized linseed oil 4%-10%, auxiliary stabilizer 1%-3%.
2. calcium zinc stabilizer as claimed in claim 1, it is characterised in that described antioxidant is four [β-(3,5-di-t-butyl 4-
Hydroxy phenyl) propanoic acid] pentaerythritol ester or β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester.
3. calcium zinc stabilizer as claimed in claim 1, it is characterised in that described brucite is organic hydrotalcite or zinc-magnesium aluminum three
Unit's houghite.
4. calcium zinc stabilizer as claimed in claim 1, it is characterised in that described auxiliary stabilizer is tetramethylolmethane or two seasons penta
Tetrol or polyvinyl alcohol or Bis(pentaerythritol).
5. the preparation method of a calcium zinc stabilizer, it is characterised in that comprise the following steps:
Step one, by calcium stearate 10%-12%, zinc stearate 4%-5%, beta-diketon 8%-10%, phosphite ester 4%-
30%, antioxidant 12%-15%, brucite 9%-16%, PE wax 13%-19%, epoxidized linseed oil 4%-10%, auxiliary are stablized
Agent 1%-3% carries out being mixed to form compound in a blending bin；
Step 2, compound is stirred in blender；
Step 3, the compound after stirring heats in a reactor, heat time heating time be ten minutes to 30 minutes, cold
Obtain product of the present invention the most afterwards.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610756484.1A CN106243462A (en) | 2016-08-30 | 2016-08-30 | Calcium zinc stabilizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610756484.1A CN106243462A (en) | 2016-08-30 | 2016-08-30 | Calcium zinc stabilizer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106243462A true CN106243462A (en) | 2016-12-21 |
Family
ID=57598363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610756484.1A Pending CN106243462A (en) | 2016-08-30 | 2016-08-30 | Calcium zinc stabilizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106243462A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467843A (en) * | 2018-10-30 | 2019-03-15 | 东莞常平金业电器制品有限公司 | A kind of PVC micelle and preparation method thereof for manufacturing medical electric wire |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429289A (en) * | 2008-11-28 | 2009-05-13 | 杭州油脂化工有限公司 | Environment-friendly calcium-zinc compound stabilizer |
| CN101942110A (en) * | 2010-09-06 | 2011-01-12 | 芜湖海螺型材科技股份有限公司 | Zn-Ca compound stabilizer |
| CN105542356A (en) * | 2016-03-04 | 2016-05-04 | 隋东阳 | Ca-Zn composite stabilizer for PVC (polyvinyl chloride) cables and preparation method of Ca-Zn composite stabilizer |
-
2016
- 2016-08-30 CN CN201610756484.1A patent/CN106243462A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429289A (en) * | 2008-11-28 | 2009-05-13 | 杭州油脂化工有限公司 | Environment-friendly calcium-zinc compound stabilizer |
| CN101942110A (en) * | 2010-09-06 | 2011-01-12 | 芜湖海螺型材科技股份有限公司 | Zn-Ca compound stabilizer |
| CN105542356A (en) * | 2016-03-04 | 2016-05-04 | 隋东阳 | Ca-Zn composite stabilizer for PVC (polyvinyl chloride) cables and preparation method of Ca-Zn composite stabilizer |
Non-Patent Citations (2)
| Title |
|---|
| 《合成材料助剂手册》编写组 编: "《合成材料助剂手册》", 30 April 1977 * |
| 郑德 等主编: "《塑料助剂系列丛书 稳定剂》", 30 June 2011 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467843A (en) * | 2018-10-30 | 2019-03-15 | 东莞常平金业电器制品有限公司 | A kind of PVC micelle and preparation method thereof for manufacturing medical electric wire |
| CN109467843B (en) * | 2018-10-30 | 2021-01-22 | 东莞常平金业电器制品有限公司 | PVC colloidal particle for manufacturing medical electric wire and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102086271B (en) | Preparation method of high-transparent high heat resistance liquid calcium-zinc heat stabilizer | |
| AU645621B2 (en) | Stabilized halogen containing polymer compositions | |
| CN102391592A (en) | Environmental-friendly calcium-zinc stabilizer for PVC (Polyvinyl Chloride) rolling film and preparation method thereof | |
| JP6243190B2 (en) | Antimicrobial metal ultrafine particle-containing dispersion and method for producing the same | |
| CN102504339A (en) | Powdery calcium-zinc complex heat stabilizer and preparation method and application thereof | |
| CN102093648A (en) | Pasty calcium-zinc composite heat stabilizer and preparation method thereof | |
| CN104877251B (en) | A kind of environmentally friendly low cigarette leadless polyvinyl chloride electrician pipe and preparation method thereof | |
| CN102516686A (en) | Environmentally-friendly efficient composite heat stabilizer for nanometer beta molecular sieve-based PVC (Polyvinyl Chloride) and preparation method thereof | |
| CN103342868A (en) | Environment-friendly ethanol migration resistance elastomer sheathing compound and preparation method thereof | |
| CN102604295B (en) | Polymer calcium zinc complex soap heat stabilizer, preparation method thereof and application thereof | |
| CN107556531A (en) | A kind of novel environment friendly stabilizer and preparation method thereof | |
| IN2014MN01307A (en) | ||
| CN101775153A (en) | Barium-zinc liquid stabilizer, preparation method and application thereof | |
| CN110106026A (en) | A kind of preparation method of acrylated epoxy soybean oil, environmentally friendly low cost PVC and its preparation method and application | |
| CN101747530B (en) | Barium-zinc liquid compound stabilizer and application thereof | |
| CN106243462A (en) | Calcium zinc stabilizer and preparation method thereof | |
| CN101717551B (en) | PVC stabilizing agent and preparation method thereof | |
| CN103408863A (en) | Infrared reflective material and membrane prepared therefrom | |
| WO2020024309A1 (en) | Composite rare earth heat stablizer for pvc and preparation method therefor | |
| CN107793691A (en) | A kind of bloom chemicals-resistant ABS/ copolyester alloy materials and preparation method thereof | |
| CN116574343A (en) | PVC environment-friendly calcium-zinc stabilizer | |
| CN103613884B (en) | PVC efficient zinc-base composite thermal stabilizer and preparation method thereof | |
| CN102516597A (en) | Special metal salt monomer for vegetable oil based liquid heat stabilizer and preparation method thereof | |
| CN104356370A (en) | Terminal polyester resin for high filler filling quantity mixed type powder coating and preparation method of terminal polyester resin | |
| CN103524945B (en) | Technology for preparing efficient environment-friendly compound heat stabilizer for polyvinyl chloride hard products |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161221 |
|
| RJ01 | Rejection of invention patent application after publication |