CN107216577A - A kind of novel PVC liquid Ca-Zn composite heat stabilizer and preparation method for adding modified Nano carbon ball - Google Patents
A kind of novel PVC liquid Ca-Zn composite heat stabilizer and preparation method for adding modified Nano carbon ball Download PDFInfo
- Publication number
- CN107216577A CN107216577A CN201710596649.8A CN201710596649A CN107216577A CN 107216577 A CN107216577 A CN 107216577A CN 201710596649 A CN201710596649 A CN 201710596649A CN 107216577 A CN107216577 A CN 107216577A
- Authority
- CN
- China
- Prior art keywords
- nano carbon
- heat stabilizer
- epoxyoleic acid
- modified nano
- carbon ball
- 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
- 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
-
- 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
-
- 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
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
-
- 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
-
- 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
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
-
- 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
-
- 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
- C08K2201/011—Nanostructured additives
-
- 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
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of novel PVC liquid Ca-Zn composite heat stabilizer and preparation method for adding modified Nano carbon ball, the present invention is using epoxyoleic acid soap as main stabilizer, modified Nano carbon ball, auxiliary heat stabilizer, phosphite ester and solvent complex is equipped with to be made, chemical modification is carried out to nano carbon microsphere using stearic acid, the surface of nano carbon microsphere is set to connect long alkyl chain, increase its oil-soluble, and the unique hexagonal structure in nano carbon microsphere surface, with excellent self-lubricating property, it is added to the abrasion resistance that tubing is remarkably improved in PVC；Using the method synthesizing epoxy oleate soap of the present invention, synthesis step is simple, product yield is high and environment is had no adverse effect, compared with traditional calcium zinc stabilizer technology of preparing, the gained weather-proof wearability of liquid Ca-Zn composite heat stabilizer of the invention is strong, long-term thermal stability agent effect is good, is not susceptible to zinc burning, has a wide range of application.
Description
Technical field
The present invention relates to calcium zinc heat stabilizer production field, and in particular to a kind of novel PVC of addition modified Nano carbon ball
With liquid Ca-Zn composite heat stabilizer and preparation method.
Background technology
Polyvinyl chloride (PVC) is the second largest synthetic resin for being only second to polyethylene, be widely used in building, telecommunication, traffic,
The industries such as electronics, chemical industry, packaging.Because PVC heat endurances are poor, softening temperature differs very little with decomposition temperature, is brought very to processing
It is big difficult, therefore must be added to a certain amount of heat stabilizer to improve its heat endurance in its process.
The Non-toxic direction of PVC heat stabilizer is concentrated mainly on organotin and Ca-Zn composite heat stabilizer two in the market
Aspect, and all make significant progress.There is price height in organic tinbase non-toxic heat stabilizer, peculiar smell is big, the Congo red time is short, meeting
The shortcomings such as generation sulfide staining, and by contrast, Ca-Zn composite heat stabilizer has more development potentiality, because Ca Zn composite
Heat stabilizer can evade Peculiar Smell, the applicability with wide spectrum, and due to being easy to customizations to develop, its cost performance is also reachable
To higher level.
Ca-Zn composite heat stabilizer can be divided into solid, liquid and paste by form.Liquid heat stabilizer is mainly used in soft
The processing of matter, transparent PVC product, liquid heat stabilizer long-term thermal stability agent effect in the market is poor.Simultaneously because liquid
Heat stabilizer is dustless during processing use, be easy to metering, easy to use, formula adjustment relatively flexible, if weather-proof, resistance to its
The performances such as mill are further modified to be improved, and its application will further expand, and market prospects are more wide.
The content of the invention
It is combined it is an object of the invention to provide a kind of novel PVC for adding modified Nano carbon ball with liquid calcium zinc thermally-stabilised
Agent and preparation method, to overcome the deficiencies in the prior art.
The object of the present invention is achieved like this：
A kind of novel PVC liquid Ca-Zn composite heat stabilizer for adding modified Nano carbon ball, it is characterised in that described is compound
Heat stabilizer includes epoxyoleic acid calcium, epoxyoleic acid zinc, modified Nano carbon ball, auxiliary heat stabilizer, phosphite ester and solvent；
Described epoxyoleic acid calcium is by epoxyoleic acid and calcium hydroxide one-step synthesis method；Described epoxyoleic acid zinc is by epoxyoleic acid and oxygen
Change zinc one-step synthesis method；Wherein described epoxyoleic acid is by oleic acid and hydrogen peroxide one-step synthesis method；Described modified Nano carbon ball
The nano carbon microsphere being modified for stearic acid grafted；Described auxiliary heat stabilizer is beta-diketon, and described solvent is tasteless kerosene, in vain
The mixture that one or more in oil, transformer oil are mixed in any proportion.
Count by weight, described -48 parts of epoxyoleic acid Ca45,10-12 parts of epoxyoleic acid zinc, modified Nano carbon ball
0.5-0.8 parts, 2-3 parts of auxiliary heat stabilizer, 10-12 parts of phosphite ester, 20-25 parts of solvent.
Described modified Nano carbon ball is made by following methods：
（1）Ball milling 1-2 hours after nano carbon microsphere and stearic acid are mixed according to mass ratio 1: 5；
（2）Said mixture is added to ultrasonic disperse 20-30min in 2mol/L sulfuric acid solution, then heated backflow 2 is small
When；
（3）By step（2）Material suction filtration while hot, be cooled to room temperature by gained sediment with cyclohexane and suction filtration for several times to washing
Unreacted stearic acid is removed, finally with deionized water rinsing to neutrality, is dried in vacuo, produces at 60 DEG C.
Oleic acid and 30% hydrogen peroxide mol ratio are 1: 3 in described epoxyoleic acid, and reaction temperature is 35-40 DEG C, reaction time
For 3-4 hours.
Described epoxyoleic acid calcium and the synthesis material of epoxyoleic acid zinc also include solvent and auxiliary agent, wherein described is molten
Agent is white oil, and consumption is epoxyoleic acid amount 85%, and described auxiliary agent is butyl, and addition is epoxyoleic acid amount
10%；The synthesis condition of described epoxyoleic acid calcium is：The mol ratio of epoxyoleic acid/calcium hydroxide is 2.6, and reaction temperature is
100-105 DEG C, the reaction time is 2 hours；The synthesis condition of described epoxyoleic acid zinc is：Aoxidize zinc overdose 7.5% (mole point
Number), the reaction time is that reaction temperature was 90-100 DEG C for 3 hours.
A kind of preparation method of the novel PVC liquid Ca-Zn composite heat stabilizer of described addition modified Nano carbon ball,
It is characterised in that it includes following steps：
（1）By weight percentage by epoxyoleic acid calcium, epoxyoleic acid zinc, modified Nano carbon ball, auxiliary heat stabilizer, phosphite ester
And solvent is prepared；
（2）Epoxyoleic acid calcium, epoxyoleic acid zinc and solvent are put into reactor, stirring is warming up to 80-90 DEG C, insulated and stirred
1-2 hours, add modified Nano carbon ball, auxiliary heat stabilizer, phosphite ester and be continuously heating to 100-110 DEG C of insulated and stirred 2-3
Hour, then constant temperature stand 6-8 hours；
（3）By step（2）Material is cooled to room temperature, depressurizes suction filtration, discharging.
The present invention has following beneficial effect：The present invention is equipped with modified Nano carbon ball, auxiliary using epoxyoleic acid soap as main stabilizer
Help heat stabilizer, phosphite ester and solvent complex to be made, chemical modification is carried out to nano carbon microsphere using stearic acid, makes nano-sized carbon
Long alkyl chain in the surface connection of ball, increases its oil-soluble, and the unique hexagonal structure in nano carbon microsphere surface, with excellent
Self-lubricating property, be added to the abrasion resistance that tubing is remarkably improved in PVC；Using the method synthesizing epoxy of the present invention
Oleate soap, synthesis step is simple, and product yield is high and environment is had no adverse effect, with traditional calcium zinc stabilizer technology of preparing phase
Than the weather-proof wearability of present invention gained liquid Ca-Zn composite heat stabilizer is strong, and long-term thermal stability agent effect is good, is not susceptible to zinc
Burn, have a wide range of application.
Embodiment
A kind of novel PVC liquid Ca-Zn composite heat stabilizer for adding modified Nano carbon ball, it is characterised in that described
Composite thermal stabilizer include epoxyoleic acid calcium, epoxyoleic acid zinc, modified Nano carbon ball, auxiliary heat stabilizer, phosphite ester and
Solvent；Described epoxyoleic acid calcium is by epoxyoleic acid and calcium hydroxide one-step synthesis method；Described epoxyoleic acid zinc is by Epoxy oil
Acid and zinc oxide one-step synthesis method；Wherein described epoxyoleic acid is by oleic acid and hydrogen peroxide one-step synthesis method；Described modification is received
Rice carbon ball is the nano carbon microsphere that stearic acid grafted is modified；Described auxiliary heat stabilizer is beta-diketon, and described solvent is tasteless
The mixture that one or more in kerosene, white oil, transformer oil are mixed in any proportion.
Count by weight, described -48 parts of epoxyoleic acid Ca45,10-12 parts of epoxyoleic acid zinc, modified Nano carbon ball
0.5-0.8 parts, 2-3 parts of auxiliary heat stabilizer, 10-12 parts of phosphite ester, 20-25 parts of solvent.
Described modified Nano carbon ball is made by following methods：
（1）Ball milling 1-2 hours after nano carbon microsphere and stearic acid are mixed according to mass ratio 1: 5；
（2）Said mixture is added to ultrasonic disperse 20-30min in 2mol/L sulfuric acid solution, then heated backflow 2 is small
When；
（3）By step（2）Material suction filtration while hot, be cooled to room temperature by gained sediment with cyclohexane and suction filtration for several times to washing
Unreacted stearic acid is removed, finally with deionized water rinsing to neutrality, is dried in vacuo, produces at 60 DEG C.
Oleic acid and 30% hydrogen peroxide mol ratio are 1: 3 in described epoxyoleic acid, and reaction temperature is 35-40 DEG C, reaction time
For 3-4 hours.
Described epoxyoleic acid calcium and the synthesis material of epoxyoleic acid zinc also include solvent and auxiliary agent, wherein described is molten
Agent is white oil, and consumption is epoxyoleic acid amount 85%, and described auxiliary agent is butyl, and addition is epoxyoleic acid amount
10%；The synthesis condition of described epoxyoleic acid calcium is：The mol ratio of epoxyoleic acid/calcium hydroxide is 2.6, and reaction temperature is
100-105 DEG C, the reaction time is 2 hours；The synthesis condition of described epoxyoleic acid zinc is：Aoxidize zinc overdose 7.5% (mole point
Number), the reaction time is that reaction temperature was 90-100 DEG C for 3 hours.
A kind of preparation method of the novel PVC liquid Ca-Zn composite heat stabilizer of described addition modified Nano carbon ball,
It is characterised in that it includes following steps：
（1）By weight percentage by epoxyoleic acid calcium, epoxyoleic acid zinc, modified Nano carbon ball, auxiliary heat stabilizer, phosphite ester
And solvent is prepared；
（2）Epoxyoleic acid calcium, epoxyoleic acid zinc and solvent are put into reactor, stirring is warming up to 80-90 DEG C, insulated and stirred
1-2 hours, add modified Nano carbon ball, auxiliary heat stabilizer, phosphite ester and be continuously heating to 100-110 DEG C of insulated and stirred 2-3
Hour, then constant temperature stand 6-8 hours；
（3）By step（2）Material is cooled to room temperature, depressurizes suction filtration, discharging.
Claims (6)
1. a kind of novel PVC liquid Ca-Zn composite heat stabilizer for adding modified Nano carbon ball, it is characterised in that described answers
Closing heat stabilizer includes epoxyoleic acid calcium, epoxyoleic acid zinc, modified Nano carbon ball, auxiliary heat stabilizer, phosphite ester and molten
Agent；Described epoxyoleic acid calcium is by epoxyoleic acid and calcium hydroxide one-step synthesis method；Described epoxyoleic acid zinc is by epoxyoleic acid
With zinc oxide one-step synthesis method；Wherein described epoxyoleic acid is by oleic acid and hydrogen peroxide one-step synthesis method；Described modified Nano
Carbon ball is the nano carbon microsphere that stearic acid grafted is modified；Described auxiliary heat stabilizer is beta-diketon, and described solvent is tasteless coal
The mixture that one or more in oil, white oil, transformer oil are mixed in any proportion.
2. a kind of novel PVC liquid Ca-Zn composite heat stabilizer for adding modified Nano carbon ball according to claim 1,
Characterized in that, count by weight, described -48 parts of epoxyoleic acid Ca45,10-12 parts of epoxyoleic acid zinc, modified Nano carbon
0.5-0.8 parts of ball, 2-3 parts of auxiliary heat stabilizer, 10-12 parts of phosphite ester, 20-25 parts of solvent.
3. a kind of novel PVC liquid Ca-Zn composite heat stabilizer for adding modified Nano carbon ball according to claim 1,
Characterized in that, described modified Nano carbon ball is made by following methods：
（1）Ball milling 1-2 hours after nano carbon microsphere and stearic acid are mixed according to mass ratio 1: 5；
（2）Said mixture is added to ultrasonic disperse 20-30min in 2mol/L sulfuric acid solution, then heated backflow 2 is small
When；
（3）By step（2）Material suction filtration while hot, be cooled to room temperature by gained sediment with cyclohexane and suction filtration for several times to washing
Unreacted stearic acid is removed, finally with deionized water rinsing to neutrality, is dried in vacuo, produces at 60 DEG C.
4. a kind of novel PVC liquid Ca-Zn composite heat stabilizer for adding modified Nano carbon ball according to claim 1,
Characterized in that, oleic acid and 30% hydrogen peroxide mol ratio are 1: 3 in described epoxyoleic acid, reaction temperature is 35-40 DEG C, reaction
Time is 3-4 hours.
5. a kind of novel PVC liquid Ca-Zn composite heat stabilizer for adding modified Nano carbon ball according to claim 1,
Characterized in that, described epoxyoleic acid calcium and the synthesis material of epoxyoleic acid zinc also include solvent and auxiliary agent, wherein described
Solvent be white oil, consumption is epoxyoleic acid amount 85%, and described auxiliary agent is butyl, and addition is epoxyoleic acid amount
10%；The synthesis condition of described epoxyoleic acid calcium is：The mol ratio of epoxyoleic acid/calcium hydroxide is 2.6, and reaction temperature is
100-105 DEG C, the reaction time is 2 hours；The synthesis condition of described epoxyoleic acid zinc is：Aoxidize zinc overdose 7.5% (mole point
Number), the reaction time is that reaction temperature was 90-100 DEG C for 3 hours.
6. a kind of novel PVC liquid Ca-Zn composite heat stabilizer for adding modified Nano carbon ball according to claim 1
Preparation method, it is characterised in that comprise the following steps：
（1）By weight percentage by epoxyoleic acid calcium, epoxyoleic acid zinc, modified Nano carbon ball, auxiliary heat stabilizer, phosphite ester
And solvent is prepared；
（2）Epoxyoleic acid calcium, epoxyoleic acid zinc and solvent are put into reactor, stirring is warming up to 80-90 DEG C, insulated and stirred
1-2 hours, add modified Nano carbon ball, auxiliary heat stabilizer, phosphite ester and be continuously heating to 100-110 DEG C of insulated and stirred 2-3
Hour, then constant temperature stand 6-8 hours；
（3）By step（2）Material is cooled to room temperature, depressurizes suction filtration, discharging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710596649.8A CN107216577A (en) | 2017-07-20 | 2017-07-20 | A kind of novel PVC liquid Ca-Zn composite heat stabilizer and preparation method for adding modified Nano carbon ball |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710596649.8A CN107216577A (en) | 2017-07-20 | 2017-07-20 | A kind of novel PVC liquid Ca-Zn composite heat stabilizer and preparation method for adding modified Nano carbon ball |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107216577A true CN107216577A (en) | 2017-09-29 |
Family
ID=59953066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710596649.8A Pending CN107216577A (en) | 2017-07-20 | 2017-07-20 | A kind of novel PVC liquid Ca-Zn composite heat stabilizer and preparation method for adding modified Nano carbon ball |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107216577A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108559129A (en) * | 2017-11-28 | 2018-09-21 | 南通新邦化工科技有限公司 | A kind of method of One-step production powder calcium zinc stabilizer |
| CN110384688A (en) * | 2019-08-14 | 2019-10-29 | 新疆农业大学 | 5 FU 5 fluorouracil oral colon-specific drug delivery system and preparation method thereof |
| CN113372619A (en) * | 2021-06-01 | 2021-09-10 | 黄山佳宝新材料科技有限公司 | High-thermal-stability liquid calcium potassium zinc stabilizer for production of foamed PVC (polyvinyl chloride) material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492236A (en) * | 2011-11-22 | 2012-06-13 | 山东瑞丰高分子材料股份有限公司 | Novel high-efficiency calcium-zinc stabilizer applied for PVC (polyvinyl chloride) section bars and preparation method thereof |
| CN102504443A (en) * | 2011-11-22 | 2012-06-20 | 山东瑞丰高分子材料股份有限公司 | Epoxidized calcium-zinc oleate compound stabilizer and preparation method thereof |
| CN102617888A (en) * | 2011-12-09 | 2012-08-01 | 江南大学 | Preparation of environment friendly calcium-zinc composite heat stabilizer and its application in PVC (polrvinyl chloride) |
| CN104530603A (en) * | 2014-12-31 | 2015-04-22 | 上海师范大学 | Epoxidized oleate-based calcium/zinc compound heat stabilizer for PVC |
-
2017
- 2017-07-20 CN CN201710596649.8A patent/CN107216577A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492236A (en) * | 2011-11-22 | 2012-06-13 | 山东瑞丰高分子材料股份有限公司 | Novel high-efficiency calcium-zinc stabilizer applied for PVC (polyvinyl chloride) section bars and preparation method thereof |
| CN102504443A (en) * | 2011-11-22 | 2012-06-20 | 山东瑞丰高分子材料股份有限公司 | Epoxidized calcium-zinc oleate compound stabilizer and preparation method thereof |
| CN102617888A (en) * | 2011-12-09 | 2012-08-01 | 江南大学 | Preparation of environment friendly calcium-zinc composite heat stabilizer and its application in PVC (polrvinyl chloride) |
| CN104530603A (en) * | 2014-12-31 | 2015-04-22 | 上海师范大学 | Epoxidized oleate-based calcium/zinc compound heat stabilizer for PVC |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108559129A (en) * | 2017-11-28 | 2018-09-21 | 南通新邦化工科技有限公司 | A kind of method of One-step production powder calcium zinc stabilizer |
| CN110384688A (en) * | 2019-08-14 | 2019-10-29 | 新疆农业大学 | 5 FU 5 fluorouracil oral colon-specific drug delivery system and preparation method thereof |
| CN110384688B (en) * | 2019-08-14 | 2023-03-17 | 新疆农业大学 | 5-fluorouracil oral colon-specific drug delivery system and preparation method thereof |
| CN113372619A (en) * | 2021-06-01 | 2021-09-10 | 黄山佳宝新材料科技有限公司 | High-thermal-stability liquid calcium potassium zinc stabilizer for production of foamed PVC (polyvinyl chloride) material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107216577A (en) | A kind of novel PVC liquid Ca-Zn composite heat stabilizer and preparation method for adding modified Nano carbon ball | |
| CN103013298B (en) | A kind of powder coating containing modified Nano carbon and preparation method thereof | |
| CN104559203A (en) | High-power high-stability cable material and preparation method thereof | |
| CN103013296A (en) | Powder coating containing modified attapulgite and preparation method of powder coating | |
| CN103865206B (en) | A kind of high temperature resistant PVC plastic pipe | |
| CN103382415B (en) | Production method of epoxidized fatty acid methyl ester/epoxidized soybean oil | |
| CN102746595B (en) | Method for preparing modified liquid metal soap thermal stabilizer through potassium ion characteristic doping | |
| CN101565512A (en) | Nanometer rare-earth calcium-zinc-magnesium-aluminum PVC composite stabilizer | |
| CN102373010A (en) | High-temperature resistant paint | |
| CN103937348A (en) | Conductive coating and preparation method thereof | |
| CN103374187A (en) | One-kettle continuously step-by-step synthesized calcium zinc composite stabilizer | |
| CN105585683A (en) | Method for preparing melamine formaldehyde resin flocculating agent | |
| CN103435944A (en) | Environment-friendly calcium-zinc composite heat stabilizer | |
| CN101805275A (en) | Method for synthesizing sodium methyl allylsulfonate | |
| CN105837631B (en) | A kind of preparation method of phosphorous modified epoxy plasticizer and obtained plasticizer | |
| CN105504399A (en) | Insulated waterproof corrosion-resistant cable laid in water body and preparation method of insulated waterproof corrosion-resistant cable | |
| CN106634418A (en) | Epoxy grafted graphene finish paint for new energy automobile and preparation method of epoxy grafted graphene finish paint | |
| CN103571108B (en) | Based on the PVC environment-friendlycomposite one package stabilizer and preparation method thereof of graphene oxide salt | |
| CN102070858A (en) | Sodium-zinc compound stabilizer for PVC and preparation method thereof | |
| CN105906985A (en) | Carbon nano tube modified plastic shell material and preparation method thereof | |
| CN102443238A (en) | Preparation method of high temperature-resistant flame-retardant cable gum material | |
| CN103897216A (en) | High-performance organic cobalt mixed salt and preparation method thereof | |
| CN110776747A (en) | Heat-insulating waterproof material and preparation method thereof | |
| CN112661721A (en) | New process for synthesizing 2-mercaptobenzothiazole zinc salt by solvent method | |
| CN102952500A (en) | Preparation method of polrvinyl chloride resin sealant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170929 |