CN106518782A - Novel preparation method of orotic acid hydrate zinc PVC stabilizer by heterogeneous system - Google Patents
Novel preparation method of orotic acid hydrate zinc PVC stabilizer by heterogeneous system Download PDFInfo
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- CN106518782A CN106518782A CN201610850188.8A CN201610850188A CN106518782A CN 106518782 A CN106518782 A CN 106518782A CN 201610850188 A CN201610850188 A CN 201610850188A CN 106518782 A CN106518782 A CN 106518782A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/52—Two oxygen atoms
- C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
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- 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
- C08K13/02—Organic and inorganic ingredients
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3462—Six-membered rings
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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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
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Abstract
By the technology of a heterogeneous system, orotic acid hydrate zinc is prepared to enhance stability of PVC. The preparation method comprises the following steps: adding proper amounts of uracil and deionized water into a four-mouth flask, heating and fully stirring, adding proper amounts of ammonia water and a phase-transfer catalyst, letting the phase-transfer catalyst be uniformly dispersed in the solution, and cooling the solution to room temperature; adding zinc pyrrolidone carboxylate and glycerol while stirring, stirring at constant temperature at room temperature for several hours, pouring the reaction solution into lots of ethanol to obtain white precipitate, separating with cold water, and washing and drying. The orotic acid hydrate zinc is used as a PVC heat stabilizer and can reduce initial coloration of PVC and prolong later zinc burning. According to the technology, cold water is used for separation and purification of the product. Thus, traditional technological flow is greatly simplified, and resource waste and environmental pollution are avoided. The raw materials are easily available, and the preparation technology is simple. Therefore, the technology has a good industrial application prospect.
Description
Technical field
The present invention relates to a kind of heterogeneous system uracil carboxylic acid zinc PVC stabilizer novel preparation method, according to the present invention
Heterogeneous system prepares new application of the uracil zinc polycarboxylate in terms of PVC thermal stabilities.
Background technology
Polyvinyl chloride accounts for the 40% of whole plastics consumption, is that yield is only second to the Equations of The Second Kind modeling of polyethylene in the world at present
Material product.But its thermal stability is poor, it is necessary to add a certain amount of heat stabilizer ability machine-shaping, to prevent or slow down PVC
Thermal degradation in process, further, it is also possible to prevent PVC product in use because the destruction that light, heat, oxygen cause is made
With keeping its physical property.Conventional PVC heat stabilizer contains metal ion with lead salts, metal soap, organic tin etc. at present
Heat stabilizer based on.With the enhancing of mankind's environmental consciousness, research and development Environment-friendlyheat heat stabilizer is just being started both at home and abroad to replace
The upsurge of traditional non-environmental protection kind.
As other chemicals, the production application of traditional heat stabilizer can also endanger human health and human survival
Environment.So, people start to start exploitation popularization non-toxic heat stabilizer to replace the upsurge of traditional poisonous kind.In this heat
In tide, the poisonous heat stabilizer such as traditional leaded, barium gradually will fade out market, and the heat of the zinc-base of environment-friendly type and organic compound base
Stabilizer will obtain the new motive force of development and the market space.It is entirely free of using organic compound as main stabilizer among these and appoints
The heat stabilizer of the organic compound base of what metal represents the long term growth direction of PVC heat stabilizer industry, develops pure organic
Main stabilizer be current thermally-stabilised research and development forefront field.
It is in existing numerous organic heat stabilizers, most of that only there is absorption HCl, complexing with catalysis PVC degradeds
The functions such as metal chloride.However, in the middle of the function of PVC heat stabilizer, replacing the ability of unstable chlorine atom to be only most critical
's.The degraded that the abilities such as HCl can only delay PVC is absorbed, and is replaced unstable chlorine atomic energy to eliminate at the very start and is caused PVC to degrade
Factor is degraded with preventing PVC.So main stabilizer must possess the ability for replacing unstable chlorine atom in PVC chains.Nitrogenous class
Organic heat stabilizers are exactly that a class has the heat stabilizer for replacing unstable chlorine atom ability, although the nitrogenous class that oneself develops at present
Heat stabilizer replaces the ability of unstable chlorine atom weaker, cannot also use as main stabilizer, but it remains organic heat
The most potential kind for developing into main stabilizer in stabilizer.
Calcium zinc heat stabilizer is the Typical Representative of nonhazardous auxiliary agent in polyvinyl chloride (PVC) industry.Also, with organotin heat
Stabilizer is compared, and calcium zinc is generally tasteless, the relatively low advantage of cost.Thus, become the important research field of PVC Auxiliaries Industries.Calcium zinc
One of research contents of heat stabilizer is while improving which to thermal stability of both PVC:Initial coloration performance and later stage
Drastically aging " zinc burning ".
There are some researches show, Chinese patent CN101717551A is prepared for a kind of self-lubricating using organic monoacid rare-earth salts, resist
Xanthochromia, the PVC stabilizer without pit, although the stabilizer has good stablizing effect, but organic monoacid rare-earth salts prepares work
Skill is complicated, and post processing power consumption is larger, relatively costly, it is impossible to industrialize.Zinc compound beyond fatty acid zinc can improve PVC
Thermal stability.For example:Using epoxyoleic acid zinc (Guo Lixin, Wan Qinghong, Cui Yanyan, China Rubber/plastics Technology and equipment, 2006,32
(12):6-9), amino-acid zinc etc. (Li Zhongbao, Liu Xiumei, plastic additive, 2010, No. 2:1-8) etc..
It is zinc-containing raw materials to improve PVC that a kind of heterogeneous system of present invention description prepares the compound of uracil zinc polycarboxylate
Thermal stability, is simplified to preparation technology, and this application scheme has no that relevant document is disclosed.
The content of the invention
A kind of preparation method of uracil carboxylic acid zinc PVC stabilizer, its molecular formula are ZnL2(NH3)2Wherein L is uracil
The ionic formula of carboxylate is:
The present invention prepares uracil zinc polycarboxylate to improve the stability of PVC using the technique of heterogeneous system, and its preparation method is:
Appropriate uracil and deionized water is added in four-hole boiling flask, is heated and is sufficiently stirred for, until uracil is completely dissolved, upwards
Appropriate ammoniacal liquor and a certain amount of phase transfer catalyst is added in stating uracil solution, and phase transfer catalyst is divided in the solution
Dissipate uniform, solution is cooled to room temperature;Under stirring, sequentially appropriate zinc pyrrolidone carboxylate and third is added in this solution
Triol, at room temperature constant temperature stirring a few hours, then pours reactant liquor in substantial amounts of ethanol into, and quickly stirs, obtain white
Precipitation.Separated, washed white precipitate with cold water again, dry to obtain purpose product.
Described heterogeneous system uracil carboxylic acid zinc PVC stabilizer novel preparation method, it is characterised in that described phase turns
Shifting catalyst is triethyl ammonium chloride(TEBA), TBAB, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate(TBAB)、
One or more in tri-n-octyl methyl ammonium chloride, DTAC and tetradecyl trimethyl ammonium chloride.
Described heterogeneous system uracil carboxylic acid zinc PVC stabilizer novel preparation method, it is characterised in that described urine is phonetic
Pyridine consumption is 50 ~ 100g.
Described heterogeneous system uracil carboxylic acid zinc PVC stabilizer novel preparation method, it is characterised in that it is described go from
Sub- water consumption is 200 ~ 500mL.
Described heterogeneous system uracil carboxylic acid zinc PVC stabilizer novel preparation method, it is characterised in that described ammoniacal liquor
Consumption is 100 ~ 300mL.
Described heterogeneous system uracil carboxylic acid zinc PVC stabilizer novel preparation method, it is characterised in that described phase turns
Shifting catalyst consumption is 0.5 ~ 1g.
Described heterogeneous system uracil carboxylic acid zinc PVC stabilizer novel preparation method, it is characterised in that described pyrroles
Alkanone zinc polycarboxylate consumption is 10 ~ 30g.
Described heterogeneous system uracil carboxylic acid zinc PVC stabilizer novel preparation method, it is characterised in that described the third three
Alcohol consumption is 50 ~ 100mL.
Described heterogeneous system uracil carboxylic acid zinc PVC stabilizer novel preparation method, it is characterised in that described ammoniacal liquor
Concentration is 15 ~ 35%.
Described heterogeneous system uracil carboxylic acid zinc PVC stabilizer novel preparation method, it is characterised in that described reaction
Temperature is 80 ~ 100 DEG C.
Beneficial effect:
Uracil zinc polycarboxylate is a kind of organo-alkali compound containing zinc, and carbon-alkoxylation displacement pi-allyl can both occur
Chlorine atom, unstable chlorine atom is eliminated from PVC macromolecular main chains;Absorption PVC can also be neutralized to discharge because of thermal degradation
HCl, play suppression PVC thermal decompositions effect.This uracil zinc polycarboxylate chemical combination that the present invention is provided effectively can change simultaneously
The initial coloring of kind PVC and long-term thermal stability performance.
By the use of heterogeneous system technique prepare uracil zinc polycarboxylate as PVC heat stabilizer, can significantly improve PVC
Thermal stability, make PVC reduce initial coloration and extend the later stage zinc burn.And the technique using cold water to product separate and
Purification, the separation and purifying technique enormously simplify traditional technological process, it is to avoid in product during separating-purifying
The wasting of resources and environmental pollution, this compound do not contain heavy metal, and raw material is easy to get, preparation process is simple.Therefore, with good work
Industry application prospect.
The preparation method of uracil zinc polycarboxylate
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
100g uracils and 500mL ionized waters is added in the four-hole boiling flask of 2L, is heated to 100 DEG C, and is sufficiently stirred for, directly
It is completely dissolved to uracil, adds 300mL ammoniacal liquor in above-mentioned uracil solution(Concentration is 15%)And 1g phase transfer catalysts four
Butylammonium bromide, solution are cooled to room temperature;Under stirring, sequentially in this solution add 30g zinc pyrrolidone carboxylates and
100mL glycerine, obtains white precipitate.At room temperature constant temperature stirring a few hours, then reactant liquor is poured in substantial amounts of ethanol,
And quickly stir, obtain white precipitate.Separated, washed white precipitate with cold water again, dry to obtain purpose product uracil zinc polycarboxylate
PVC stabilizer.
Embodiment 1
100 parts of PVC, 50 parts of dioctyl phthalate, 30 parts of calcium carbonate, 0.2 part of three (2,4- di-t-butyls of phosphorous acid
Phenyl) ester and 2 parts of calcium stearates, the mixture on a mill under conditions of 180 DEG C of the drying of 2 parts of uracil zinc polycarboxylate compositions
Roll-in 5min.Compressing tablet, is cut into 2cm × 2cm blockage samples after taking piece, require according to GB/T 7141-92 standards, PVC pieces are pressed
Sequential packet is placed in ageing oven, carries out oven ageing experiment test at 190 ± 1 DEG C, takes out test piece, observation every 10 min
And the change of test piece colourity is recorded, according to ASTM D1925-70, its yellowness index is recorded, 1 is the results are shown in Table.
Embodiment 2:
100 parts of PVC, 50 parts of dioctyl phthalate, 30 parts of calcium carbonate, 0.2 part of three (2,4- di-t-butyls of phosphorous acid
Phenyl) ester and 2 parts of calcium stearates, 2 parts of uracil zinc polycarboxylates, mixtures of the drying of 0.2 part of dibenzoyl methane composition opening
Roll-in 5min under conditions of 180 DEG C in mill.Compressing tablet, is cut into 2cm × 2cm blockage samples, according to GB/T 7141- after taking piece
92 standards require, PVC pieces are grouped in order and are placed in ageing oven, carry out oven ageing experiment test, often at 190 ± 1 DEG C
Test piece is taken out every 10 min, the change of test piece colourity is observed and record, till being continued until that black occurs in test piece, according to
ASTM D1925-70, record its yellowness index, the results are shown in Table 1.
Embodiment 3:
100 parts of PVC, 50 parts of dioctyl phthalate, 30 parts of calcium carbonate, 0.2 part of three (2,4- di-t-butyls of phosphorous acid
Phenyl) ester and 2 parts of calcium stearates, 2 parts of uracil zinc polycarboxylates, the drying of 0.2 part of 1,3- dimethyl -6- aminopyrimidines composition
Mixture roll-in 5min under conditions of 180 DEG C on a mill.Compressing tablet, is cut into 2cm × 2cm blockage samples after taking piece, according to
GB/T 7141-92 standards require, PVC pieces are grouped in order and are placed in ageing oven, carry out oven ageing reality at 190 ± 1 DEG C
Test is tried, and is taken out test piece every 10 min, is observed and record the change of test piece colourity, is continued until that test piece black occurs and is
Only, according to ASTM D1925-70, its yellowness index is recorded, 1 is the results are shown in Table.
Comparative example 4:
By 100 parts of PVC, 50 parts of dioctyl phthalates, 0.2 part of three (2,4- di-tert-butyl-phenyl) ester of phosphorous acid and 2 parts are hard
Resin acid zinc, the mixture roll-in 5min under conditions of 180 DEG C on a mill of the drying of 2 parts of calcium stearates composition.Compressing tablet, takes piece
After be cut into 2cm × 2cm blockage samples, according to GB/T 7141-92 standards require, PVC pieces are grouped in order and are placed in aging baking
In case, oven ageing experiment test at 190 ± 1 DEG C, is carried out, test piece is taken out every 10 min, observe and record the change of test piece colourity
Change, according to ASTM D1925-70, record its yellowness index, the results are shown in Table 1.
Impact of the PVC stabilizer of 1. different process of table and species to PVC yellowness indexs
Time/min | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 | 100 |
Embodiment 1 | 6.18 | 8.94 | 14.56 | 19.65 | 28.94 | 39.45 | 41.75 | 45.23 | 49.25 | 52.34 |
Embodiment 2 | 3.96 | 5.76 | 8.56 | 14.48 | 24.21 | 29.33 | 35.44 | 45.37 | 52.36 | 58.64 |
Embodiment 3 | 5.16 | 7.28 | 13.96 | 16.37 | 26.24 | 39.48 | 46.68 | 46.26 | 50.52 | 57.11 |
Comparative example 4 | 10.56 | 12.34 | 19.56 | 26.35 | 30.65 | 41.32 | 49.74 | 55.36 | 63.66 | 69.25 |
Uracil zinc polycarboxylate can be seen that with than the more preferable suppression of zinc stearate by embodiment 1 in table 1 and the contrast of comparative example 4
First discolouration ability processed and prolongation thermal decomposition ability.
By embodiment 1 in table 1 and embodiment 2 contrast as can be seen that uracil zinc polycarboxylate have with dibenzoyl methane it is bright
Aobvious synergy.
Contrasted with embodiment 3 as can be seen that uracil zinc polycarboxylate serves 1,3- to a great extent by 1 embodiment 1 of table
The effect of dimethyl -6- aminopyrimidines.
The structural characterization of product:Nmr analysis
Take a certain amount of uracil zinc polycarboxylate and PVC stirs, be then added to 180010 points are kneaded in the two-roll mill of C
Clock.As PVC can be dissolved in tetrahydrofuran, uracil zinc polycarboxylate is insoluble, so washing mixing materials of muttering of being barked using tetrahydrochysene, are washed repeatedly
Wash 4 times to wash away PVC completely.Remaining uracil zinc polycarboxylate distilled water makees hydrogen nuclear magnetic resonance analysis of spectrum after cleaning drying, its
As a result it is as shown in Figure 1.
Description of the drawings:
Fig. 1. the structural characterization of uracil zinc polycarboxylate
As can be seen from Figure 1 the nuclear-magnetism figure has a wider absorption at 1.9-2.6ppm and 4.2-4.7ppm two respectively
The peak ,-CH in the absworption peak at 1.9-2.6ppm is PVC segments2The absworption peak of hydrogen atom on-group, and in 4.2-4.7ppm
Place be hydrogen atom on-CHCl- groups in PVC segments absworption peak.This shows to connect by chemical bond in the own Jing of PVC segments
It has been connected on uracil zinc polycarboxylate molecule, this illustrates that uracil zinc polycarboxylate can be sent out by replacing the unstable group in PVC
Wave stabilization.
Claims (11)
1. heterogeneous system uracil carboxylic acid zinc PVC stabilizer novel preparation method, its molecular formula are as follows:ZnL2(NH3)2Its
Middle L is that the ionic formula of uracil carboxylate radical is:
。
2. the heterogeneous system uracil carboxylic acid zinc PVC stabilizer novel preparation method according to claims 1, its feature exist
In carrying out as steps described below:Appropriate uracil and deionized water is added in four-hole boiling flask, is heated and is sufficiently stirred for, until
Uracil is completely dissolved, and adds appropriate ammoniacal liquor and a certain amount of phase transfer catalyst, and make phase in above-mentioned uracil solution
Transfer catalyst is uniformly dispersed in the solution, and solution is cooled to room temperature;Under stirring, sequentially add in right amount in this solution
Zinc pyrrolidone carboxylate and glycerine, at room temperature constant temperature stirring a few hours, then reactant liquor is poured in substantial amounts of ethanol,
And quickly stir, white precipitate is obtained, then separated, washed white precipitate with cold water, dry to obtain purpose product.
3. the heterogeneous system uracil carboxylic acid zinc PVC stabilizer novel preparation method according to claims 2, its feature exist
In described phase transfer catalyst be triethyl ammonium chloride(TEBA), TBAB, tetrabutylammonium chloride, tetrabutyl sulfuric acid
Hydrogen ammonium(TBAB), tri-n-octyl methyl ammonium chloride, in DTAC and tetradecyl trimethyl ammonium chloride one
Plant or several.
4. the heterogeneous system uracil carboxylic acid zinc PVC stabilizer novel preparation method according to claims 2, its feature exist
In described uracil consumption be 50 ~ 100g.
5. the heterogeneous system uracil carboxylic acid zinc PVC stabilizer novel preparation method according to claims 2, its feature exist
In described deionized water consumption be 200 ~ 500mL.
6. the heterogeneous system uracil carboxylic acid zinc PVC stabilizer novel preparation method according to claims 2, its feature exist
In described ammonia volume be 100 ~ 300mL.
7. the heterogeneous system uracil carboxylic acid zinc PVC stabilizer novel preparation method according to claims 2, its feature exist
In described phase transfer catalyst consumption be 0.5 ~ 1g.
8. the heterogeneous system uracil carboxylic acid zinc PVC stabilizer novel preparation method according to claims 2, its feature exist
In described zinc pyrrolidone carboxylate consumption be 10 ~ 30g.
9. the heterogeneous system uracil carboxylic acid zinc PVC stabilizer novel preparation method according to claims 2, its feature exist
In described glycerine consumption be 50 ~ 100mL.
10. the heterogeneous system uracil carboxylic acid zinc PVC stabilizer novel preparation method according to claims 2, its feature
It is that described ammonia concn is 15 ~ 35%.
The 11. heterogeneous system uracil carboxylic acid zinc PVC stabilizer novel preparation methods according to claims 2, its feature
Reaction temperature described in being is 80 ~ 100 DEG C.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN114835651A (en) * | 2022-05-05 | 2022-08-02 | 横店集团得邦工程塑料有限公司 | Preparation method of high-transparency PVC heat stabilizer and application of high-transparency PVC heat stabilizer in soft transparent PVC plates |
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CN103183690A (en) * | 2011-12-31 | 2013-07-03 | 深圳市志海实业有限公司 | Calcium zinc heat stabilizer used for PVC, zinc-containing compound and application |
CN103183644A (en) * | 2011-12-31 | 2013-07-03 | 深圳市志海实业有限公司 | Uracil zinc salt and application thereof as heat stabilizer for PVC |
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2016
- 2016-09-26 CN CN201610850188.8A patent/CN106518782A/en active Pending
Patent Citations (2)
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CN103183690A (en) * | 2011-12-31 | 2013-07-03 | 深圳市志海实业有限公司 | Calcium zinc heat stabilizer used for PVC, zinc-containing compound and application |
CN103183644A (en) * | 2011-12-31 | 2013-07-03 | 深圳市志海实业有限公司 | Uracil zinc salt and application thereof as heat stabilizer for PVC |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN114835651A (en) * | 2022-05-05 | 2022-08-02 | 横店集团得邦工程塑料有限公司 | Preparation method of high-transparency PVC heat stabilizer and application of high-transparency PVC heat stabilizer in soft transparent PVC plates |
CN114835651B (en) * | 2022-05-05 | 2023-08-29 | 横店集团得邦工程塑料有限公司 | Preparation method of high-transparency PVC heat stabilizer and application of high-transparency PVC heat stabilizer in soft transparent PVC plate |
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Application publication date: 20170322 |