CN110437395A - The preparation method of cross-linking type function polyacrylate polymers in a kind of oil-soluble low temperature - Google Patents
The preparation method of cross-linking type function polyacrylate polymers in a kind of oil-soluble low temperature Download PDFInfo
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- CN110437395A CN110437395A CN201910633653.6A CN201910633653A CN110437395A CN 110437395 A CN110437395 A CN 110437395A CN 201910633653 A CN201910633653 A CN 201910633653A CN 110437395 A CN110437395 A CN 110437395A
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Abstract
The invention belongs to technical field of polymer preparation, the preparation method for specifically disclosing cross-linking type function polyacrylate polymers in a kind of oil-soluble low temperature into the material resin and then polymerize the polyacrylate copolymer of acquisition including the material resin based on polyamide or polyvinyl resin and by absorbing propenoic acid ester monomer, dissolution monomer, function monomer and polymerization initiator；By adding special dissolution monomer, the dissolution monomer is using nitrate as key bridge, the ethylenically unsaturated monomer containing carboxylic acid functional is bonded with water-soluble polymer by being grafted, and compound composition is adsorbed with thixotropic agent, chaotropic agent is in water-soluble solvent by Influence of Electrolyte, electrophoresis can be established with each anionoid, the cation of polyacrylate polymers, it can accelerate the movement of polyacrylate polymers particle without stirring in water-soluble solvent, it is ensured that polyacrylate polymers do not settle while being added to the water quickly movement dissolution.
Description
Technical field
The invention belongs to technical field of polymer preparation, and in particular to cross-linking type function polypropylene in a kind of oil-soluble low temperature
The preparation method of acid ester polymer.
Background technique
Using esters of acrylic acid as the homopolymer of monomer or copolymer, R, R' are substituent group, and substituent group is different, polymer property
Also different, acrylate is very easy to polymerization under the effect of light, heat and initiator, and polyacrylate is soluble in acetone, acetic acid second
Ester, benzene and dichloroethanes, and it is not soluble in water, and due to the flexibility of its macromolecular chain, their glass transition temperature is lower, and with ester
The carbon atom number and its branching situation of base and it is different, when carbon atom number be 8 when it is minimum, in the ester group of same carbon atoms number, branching
Person's glass transition temperature is higher, has excellent light with the acrylic acid ester emulsion that acrylic acid or esters of acrylic acid are main Material synthesis
Stability and weatherability, good water-fast, alkaline-resisting, chemical resistance and adhesive property, therefore be widely used as adhesive, apply
Expect film forming agent and daily-use chemical industry, electrochmical power source, functional membrane, medical high polymer, nano material and water process etc., still
There is low temperature to become fragile for acrylic acid ester emulsion, high temperature becomes glutinous the disadvantages of losing strong, easy after tack, limits its application range and use
Value.
Chinese patent discloses the polymer based on polyacrylate, and Publication No. CN101307168A is realized and is based on
The polymer of polyacrylate has fabulous mechanical performance, but traditional polyacrylate polymers are directed to low-temperature self-crosslinking
There are still the defects for being limited to polymerize in water-soluble solvent for polymerization.
Summary of the invention
The purpose of the present invention is to provide a kind of preparations of cross-linking type function polyacrylate polymers in oil-soluble low temperature
Method, to solve the problems mentioned in the above background technology.
To achieve the above object, present invention employs following technical solutions: cross-linking type function is poly- in a kind of oil-soluble low temperature
Acrylate polymer including the material resin based on polyamide or polyvinyl resin and passes through absorbing propenoic acid ester monomer, rush
Molten monomer, function monomer and polymerization initiator into the material resin and then polymerize the polyacrylate copolymer of acquisition, institute
The mixture that function monomer is selected from acrylic acid, methacrylic acid and acrylic acid and methacrylic acid is stated, wherein every 50 parts by weight institute
The polyacrylate copolymer for dispersing 60-500 parts by weight in material resin is stated, the dissolution monomer is selected to be made with nitrate
For key bridge, the ethylenically unsaturated monomer containing carboxylic acid functional is bonded with water-soluble polymer by being grafted, and with touching
Become agent and adsorbs compound composition.
Preferably, the resin based on polyethylene be polyethylene and ethylene copolymers, with functional group as branch polyethylene,
Or the mixture of above-mentioned substance, it is described that have functional group as the polyethylene of branch be poly- (ethylene-co-propylene -co- diene),
The acrylate monomer is the mixture of alkyl acrylate monomer, alkyl methacrylate monomer.
Preferably, the polyacrylate copolymer is by absorbing propenoic acid ester monomer and polymerization initiator to comprising dividing
In the material resin for dissipating polyamide or polyvinyl resin in water, and subsequent first polymerized monomer and absorbing propenoic acid ester list
Body, function monomer and polymerization initiator to by first polymerize in product obtained and subsequent second polymerized monomer and formed.
The preparation method of cross-linking type function polyacrylate polymers in a kind of oil-soluble low temperature, comprising the following steps:
First polymerization procedure
S1, firstly, by water, material resin, acrylate monomer, dissolution monomer, function monomer and polymerization initiator add
Into the reactor equipped with blender, heater and cooler, reactor is then sealed；
The summation of S2, molecule amount based on acrylate monomer, dissolution monomer, function monomer and polymerization initiator, can
To use the polymerization initiator of 0.5-2.0mol% to be added dropwise in reactor, feed time is 60 minutes；
High pressure nitrogen is input in the reactor of sealing by S3, then while stirring charging, then release so that
Except deoxidation from reactor；
S4, the absorption temperature that the temperature of reactor is increased to 50-100 DEG C according to selected polymerization initiator, Zhi Houbing
Olefin(e) acid ester monomer, dissolution monomer, function monomer and polymerization initiator are absorbed into material resin, the type based on material resin
With the type of acrylate monomer, need to absorb 2-4 hours；
S5, acrylate monomer, function monomer and polymerization initiator are absorbed into material resin pellet, by reacting
Them are stirred in device together with water and increases temperature, causes the decomposition of polymerization initiator and the polymerization of monomer；
S6, the temperature in reactor, institute in material resin are adjusted according to the decomposition temperature appropriate of polymerization initiator used
Acrylate monomer, function monomer and the polymerization initiator of absorption start polymerization reaction in pellet, and it is total to form polyacrylate
Polymers needs 3-8 hours polymerization reaction times according to the type of material resin, monomer and polymerization initiator；
S7, it after terminating level-one polymerization reaction, is fully cooled reactor and filters out reaction mixture, obtain level-one polymerization
Object cleans level-one polymer more than once with warm water, the dry level-one in the case where being suitable for the drying condition of raw materials used resin and monomer
Polymer, and fully remove water；
Second polymerization procedure
S1, polymer product, acrylate monomer, function monomer and the polymerization initiator of the first polymerization preparation are added together
Enter into reactor, by with first polymerize it is identical in a manner of carry out the second polymerization；
S2, the molecule amount of acrylate monomer, function monomer and polymerization initiator used based on the second polymerization it is total
With the polymerization initiator of 0.5-2.0mol% can be used；
When S3, polymerization reaction are completed, it is sufficiently cool reactor and obtains pellet by filtering out reaction mixture,
It fully dries pellet obtained and fully removes water, obtain the gathering based on polyacrylate being dispersed in material resin
Close object.
Technical effect and advantage of the invention: compared with prior art, the invention proposes it is a kind of can be in soluble solvent
The novel processing step being polymerize, this method is by adding special dissolution monomer, and the dissolution monomer is using nitrate as key
Ethylenically unsaturated monomer containing carboxylic acid functional is bonded by bridge by being grafted with water-soluble polymer, and and thixotropic agent
Adsorb compound composition, chaotropic agent in water-soluble solvent by Influence of Electrolyte, can with all kinds of yin of polyacrylate polymers from
Son, cation establish electrophoresis, can accelerate the movement of polyacrylate polymers particle without stirring in water-soluble solvent, really
It protects while polyacrylate polymers are added to the water quickly movement dissolution and does not settle, there is extensive market application value, together
The charging technology of Shi Caiyong special dropwise addition mode has prepared cross-linking type function polymeric acrylic acid polyisocyanate polyaddition in oil-soluble low temperature
Object.
Specific embodiment
Technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is only
It is a part of the embodiment of the present invention, instead of all the embodiments.Specific embodiment described herein is only used to explain this
Invention, is not intended to limit the present invention.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creation
Property labour under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
Embodiment 1
The present invention provides cross-linking type function polyacrylate polymers in a kind of oil-soluble low temperature, including are based on polyamide
Or polyvinyl resin material resin and arrived by absorbing propenoic acid ester monomer, dissolution monomer, function monomer and polymerization initiator
In the material resin and then polymerize the polyacrylate copolymer of acquisition, function monomer be selected from acrylic acid, methacrylic acid and
The mixture of acrylic acid and methacrylic acid, wherein the polyacrylate for dispersing 60 parts by weight in every 50 raw material resin is total
Polymers, dissolution monomer are selected from using nitrate as key bridge, by grafting by the ethylenically unsaturated monomer containing carboxylic acid functional and
Water-soluble polymer is bonded, and adsorbs compound composition with thixotropic agent.
Specifically, the resin based on polyethylene is polyethylene and ethylene copolymers, it is poly- for having functional group as the polyethylene of branch
(ethylene-co-propylene -co- diene), acrylate monomer is alkyl acrylate monomer, alkyl methacrylate monomer
Mixture.
Specifically, polyacrylate copolymer is by absorbing propenoic acid ester monomer and polymerization initiator to comprising being dispersed in
Polyamide in water or in the material resin of polyvinyl resin, and subsequent first polymerized monomer and absorbing propenoic acid ester monomer, function
Can monomer and polymerization initiator to by first polymerize in product obtained and subsequent second polymerized monomer and formed.
The preparation method of cross-linking type function polyacrylate polymers in a kind of oil-soluble low temperature, comprising the following steps:
First polymerization procedure
S1, firstly, by water, material resin, acrylate monomer, dissolution monomer, function monomer and polymerization initiator add
Into the reactor equipped with blender, heater and cooler, reactor is then sealed；
The summation of S2, molecule amount based on acrylate monomer, dissolution monomer, function monomer and polymerization initiator, can
To use the polymerization initiator of 0.5mol% to be added dropwise in reactor, feed time is 60 minutes；
High pressure nitrogen is input in the reactor of sealing by S3, then while stirring charging, then release so that
Except deoxidation from reactor；
S4, the absorption temperature that the temperature of reactor is increased to 50 DEG C according to selected polymerization initiator, later acrylic acid
Ester monomer, dissolution monomer, function monomer and polymerization initiator are absorbed into material resin, the type based on material resin and third
The type of olefin(e) acid ester monomer needs to absorb 2 hours；
S5, acrylate monomer, function monomer and polymerization initiator are absorbed into material resin pellet, by reacting
Them are stirred in device together with water and increases temperature, causes the decomposition of polymerization initiator and the polymerization of monomer；
S6, the temperature in reactor, institute in material resin are adjusted according to the decomposition temperature appropriate of polymerization initiator used
Acrylate monomer, function monomer and the polymerization initiator of absorption start polymerization reaction in pellet, and it is total to form polyacrylate
Polymers needs 3 hours polymerization reaction times according to the type of material resin, monomer and polymerization initiator；
S7, it after terminating level-one polymerization reaction, is fully cooled reactor and filters out reaction mixture, obtain level-one polymerization
Object cleans level-one polymer more than once with warm water, the dry level-one in the case where being suitable for the drying condition of raw materials used resin and monomer
Polymer, and fully remove water；
Second polymerization procedure
S1, polymer product, acrylate monomer, function monomer and the polymerization initiator of the first polymerization preparation are added together
Enter into reactor, by with first polymerize it is identical in a manner of carry out the second polymerization；
S2, the molecule amount of acrylate monomer, function monomer and polymerization initiator used based on the second polymerization it is total
With the polymerization initiator of 0.5mol% can be used；
When S3, polymerization reaction are completed, it is sufficiently cool reactor and obtains pellet by filtering out reaction mixture,
It fully dries pellet obtained and fully removes water, obtain the gathering based on polyacrylate being dispersed in material resin
Close object.
Embodiment 2
The present invention provides cross-linking type function polyacrylate polymers in a kind of oil-soluble low temperature, including are based on polyamide
Or polyvinyl resin material resin and arrived by absorbing propenoic acid ester monomer, dissolution monomer, function monomer and polymerization initiator
In the material resin and then polymerize the polyacrylate copolymer of acquisition, function monomer be selected from acrylic acid, methacrylic acid and
The mixture of acrylic acid and methacrylic acid, wherein dispersing the polyacrylate of 300 parts by weight in every 50 raw material resin
Copolymer, dissolution monomer is selected from using nitrate as key bridge, by being grafted the ethylenically unsaturated monomer containing carboxylic acid functional
It is bonded with water-soluble polymer, and adsorbs compound composition with thixotropic agent.
Specifically, the resin based on polyethylene is the polyethylene for having functional group as branch, have functional group as branch
The polyethylene of chain is poly- (ethylene-co-propylene), and acrylate monomer is alkyl methacrylate monomer.
Specifically, polyacrylate copolymer is by absorbing propenoic acid ester monomer and polymerization initiator to comprising being dispersed in
Polyamide in water or in the material resin of polyvinyl resin, and subsequent first polymerized monomer and absorbing propenoic acid ester monomer, function
Can monomer and polymerization initiator to by first polymerize in product obtained and subsequent second polymerized monomer and formed.
The preparation method of cross-linking type function polyacrylate polymers in a kind of oil-soluble low temperature, comprising the following steps:
First polymerization procedure
S1, firstly, by water, material resin, acrylate monomer, dissolution monomer, function monomer and polymerization initiator add
Into the reactor equipped with blender, heater and cooler, reactor is then sealed；
The summation of S2, molecule amount based on acrylate monomer, dissolution monomer, function monomer and polymerization initiator, can
To use the polymerization initiator of 1.0mol% to be added dropwise in reactor, feed time is 60 minutes；
High pressure nitrogen is input in the reactor of sealing by S3, then while stirring charging, then release so that
Except deoxidation from reactor；
S4, the absorption temperature that the temperature of reactor is increased to 80 DEG C according to selected polymerization initiator, later acrylic acid
Ester monomer, dissolution monomer, function monomer and polymerization initiator are absorbed into material resin, the type based on material resin and third
The type of olefin(e) acid ester monomer needs to absorb 3 hours；
S5, acrylate monomer, function monomer and polymerization initiator are absorbed into material resin pellet, by reacting
Them are stirred in device together with water and increases temperature, causes the decomposition of polymerization initiator and the polymerization of monomer；
S6, the temperature in reactor, institute in material resin are adjusted according to the decomposition temperature appropriate of polymerization initiator used
Acrylate monomer, function monomer and the polymerization initiator of absorption start polymerization reaction in pellet, and it is total to form polyacrylate
Polymers needs 3-8 hours polymerization reaction times according to the type of material resin, monomer and polymerization initiator；
S7, it after terminating level-one polymerization reaction, is fully cooled reactor and filters out reaction mixture, obtain level-one polymerization
Object cleans level-one polymer more than once with warm water, the dry level-one in the case where being suitable for the drying condition of raw materials used resin and monomer
Polymer, and fully remove water；
Second polymerization procedure
S1, polymer product, acrylate monomer, function monomer and the polymerization initiator of the first polymerization preparation are added together
Enter into reactor, by with first polymerize it is identical in a manner of carry out the second polymerization；
S2, the molecule amount of acrylate monomer, function monomer and polymerization initiator used based on the second polymerization it is total
With the polymerization initiator of 1.0mol% can be used；
When S3, polymerization reaction are completed, it is sufficiently cool reactor and obtains pellet by filtering out reaction mixture,
It fully dries pellet obtained and fully removes water, obtain the gathering based on polyacrylate being dispersed in material resin
Close object.
Embodiment 3
The present invention provides cross-linking type function polyacrylate polymers in a kind of oil-soluble low temperature, including are based on polyamide
Or polyvinyl resin material resin and arrived by absorbing propenoic acid ester monomer, dissolution monomer, function monomer and polymerization initiator
In the material resin and then polymerize the polyacrylate copolymer of acquisition, function monomer be selected from acrylic acid, methacrylic acid and
The mixture of acrylic acid and methacrylic acid, wherein dispersing the polyacrylate of 500 parts by weight in every 50 raw material resin
Copolymer, dissolution monomer is selected from using nitrate as key bridge, by being grafted the ethylenically unsaturated monomer containing carboxylic acid functional
It is bonded with water-soluble polymer, and adsorbs compound composition with thixotropic agent.
It is mixed with functional group as the polyethylene of branch specifically, the resin based on polyethylene is polyethylene and ethylene copolymers
Object is closed, having functional group as the polyethylene of branch is poly- (ethylene-co-propylene), and acrylate monomer is alkyl acrylate
Monomer.
Specifically, polyacrylate copolymer is by absorbing propenoic acid ester monomer and polymerization initiator to comprising being dispersed in
Polyamide in water or in the material resin of polyvinyl resin, and subsequent first polymerized monomer and absorbing propenoic acid ester monomer, function
Can monomer and polymerization initiator to by first polymerize in product obtained and subsequent second polymerized monomer and formed.
The preparation method of cross-linking type function polyacrylate polymers in a kind of oil-soluble low temperature, comprising the following steps:
First polymerization procedure
S1, firstly, by water, material resin, acrylate monomer, dissolution monomer, function monomer and polymerization initiator add
Into the reactor equipped with blender, heater and cooler, reactor is then sealed；
The summation of S2, molecule amount based on acrylate monomer, dissolution monomer, function monomer and polymerization initiator, can
To use the polymerization initiator of 2.0mol% to be added dropwise in reactor, feed time is 60 minutes；
High pressure nitrogen is input in the reactor of sealing by S3, then while stirring charging, then release so that
Except deoxidation from reactor；
S4, the absorption temperature that the temperature of reactor is increased to 100 DEG C according to selected polymerization initiator, later acrylic acid
Ester monomer, dissolution monomer, function monomer and polymerization initiator are absorbed into material resin, the type based on material resin and third
The type of olefin(e) acid ester monomer needs to absorb 4 hours；
S5, acrylate monomer, function monomer and polymerization initiator are absorbed into material resin pellet, by reacting
Them are stirred in device together with water and increases temperature, causes the decomposition of polymerization initiator and the polymerization of monomer；
S6, the temperature in reactor, institute in material resin are adjusted according to the decomposition temperature appropriate of polymerization initiator used
Acrylate monomer, function monomer and the polymerization initiator of absorption start polymerization reaction in pellet, and it is total to form polyacrylate
Polymers needs 3-8 hours polymerization reaction times according to the type of material resin, monomer and polymerization initiator；
S7, it after terminating level-one polymerization reaction, is fully cooled reactor and filters out reaction mixture, obtain level-one polymerization
Object cleans level-one polymer more than once with warm water, the dry level-one in the case where being suitable for the drying condition of raw materials used resin and monomer
Polymer, and fully remove water；
Second polymerization procedure
S1, polymer product, acrylate monomer, function monomer and the polymerization initiator of the first polymerization preparation are added together
Enter into reactor, by with first polymerize it is identical in a manner of carry out the second polymerization；
S2, the molecule amount of acrylate monomer, function monomer and polymerization initiator used based on the second polymerization it is total
With the polymerization initiator of 2.0mol% can be used；
When S3, polymerization reaction are completed, it is sufficiently cool reactor and obtains pellet by filtering out reaction mixture,
It fully dries pellet obtained and fully removes water, obtain the gathering based on polyacrylate being dispersed in material resin
Close object.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features,
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (4)
1. cross-linking type function polyacrylate polymers in a kind of oil-soluble low temperature, it is characterised in that: including based on polyamide or
The material resin of polyvinyl resin and by absorbing propenoic acid ester monomer, dissolution monomer, function monomer and polymerization initiator arrive this
In material resin and then it polymerize the polyacrylate copolymer of acquisition, the function monomer is selected from acrylic acid, methacrylic acid
With the mixture of acrylic acid and methacrylic acid, wherein in material resin described in every 50 parts by weight disperse 60-500 parts by weight institute
Polyacrylate copolymer is stated, the dissolution monomer is selected from using nitrate as key bridge, will contain carboxylic acid functional by grafting
Ethylenically unsaturated monomer be bonded with water-soluble polymer, and adsorb compound composition with thixotropic agent.
2. cross-linking type function polyacrylate polymers in a kind of oil-soluble low temperature according to claim 1, feature exist
In: the resin based on polyethylene is polyethylene and ethylene copolymers, polyethylene or above-mentioned substance with functional group as branch
Mixture, it is described have functional group as the polyethylene of branch be poly- (ethylene -co- 1- butylene), poly- (ethylene-co-propylene) or
Poly- (ethylene-co-propylene -co- diene), the acrylate monomer is alkyl acrylate monomer, alkyl methacrylate
The mixture of monomer or above-mentioned substance.
3. cross-linking type function polyacrylate polymers in a kind of oil-soluble low temperature according to claim 2, feature exist
In: the polyacrylate copolymer is to be gathered by absorbing propenoic acid ester monomer and polymerization initiator to comprising what is be dispersed in water
In the material resin of amide or polyvinyl resin, and with the first polymerized monomer and absorbing propenoic acid ester monomer, function monomer and gather
Initiator is closed to be formed in by the first polymerization product obtained and with the second polymerized monomer.
4. the preparation method of cross-linking type function polyacrylate polymers in a kind of oil-soluble low temperature, it is characterised in that: including with
Lower step:
First polymerization procedure
S1, match firstly, water, material resin, acrylate monomer, dissolution monomer, function monomer and polymerization initiator are added to
In the reactor for having blender, heater and cooler, reactor is then sealed；
The summation of S2, molecule amount based on acrylate monomer, dissolution monomer, function monomer and polymerization initiator, can make
It is added dropwise in reactor with the polymerization initiator of 0.5-2.0mol%, feed time is 60 minutes；
High pressure nitrogen is input in the reactor of sealing by S3, then while stirring charging, is then released so that from anti-
It answers in device except deoxidation；
S4, the absorption temperature that the temperature of reactor is increased to 50-100 DEG C according to selected polymerization initiator, later acrylic acid
Ester monomer, dissolution monomer, function monomer and polymerization initiator are absorbed into material resin, the type based on material resin and third
The type of olefin(e) acid ester monomer needs to absorb 2-4 hours；
S5, acrylate monomer, function monomer and polymerization initiator are absorbed into material resin pellet, by the reactor
Them are stirred together with water and increases temperature, cause the decomposition of polymerization initiator and the polymerization of monomer；
S6, the temperature in reactor is adjusted according to the decomposition temperature appropriate of polymerization initiator used, absorbed in material resin
Acrylate monomer, function monomer and polymerization initiator start polymerization reaction in pellet, form polyacrylate copolymer,
According to the type of material resin, monomer and polymerization initiator, 3-8 hours polymerization reaction times are needed；
S7, it after terminating level-one polymerization reaction, is fully cooled reactor and filters out reaction mixture, obtain level-one polymer, use
Warm water cleans level-one polymer more than once, the dry level-one polymerization in the case where being suitable for the drying condition of raw materials used resin and monomer
Object, and fully remove water；
Second polymerization procedure
S1, polymer product, acrylate monomer, function monomer and the polymerization initiator of the first polymerization preparation are added to together
In reactor, by with first polymerize it is identical in a manner of carry out the second polymerization；
The summation of S2, the molecule amount for polymerizeing the acrylate monomer, function monomer and the polymerization initiator that use based on second, can
To use the polymerization initiator of 0.5-2.0mol%；
When S3, polymerization reaction are completed, it is sufficiently cool reactor and obtains pellet by filtering out reaction mixture, sufficiently
The dry pellet obtained in ground simultaneously fully removes water, obtains the polymerization based on polyacrylate being dispersed in material resin
Object.
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| CN201910633653.6A CN110437395A (en) | 2019-07-15 | 2019-07-15 | The preparation method of cross-linking type function polyacrylate polymers in a kind of oil-soluble low temperature |
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| CN201910633653.6A CN110437395A (en) | 2019-07-15 | 2019-07-15 | The preparation method of cross-linking type function polyacrylate polymers in a kind of oil-soluble low temperature |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101307168A (en) * | 2007-05-18 | 2008-11-19 | 普力摩尔斯奈特株式会社 | Polyacrylate-based polymer |
| CN103922836A (en) * | 2014-03-21 | 2014-07-16 | 成都新柯力化工科技有限公司 | Water soluble fertilizer dissolving promoter and its preparation method |
-
2019
- 2019-07-15 CN CN201910633653.6A patent/CN110437395A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101307168A (en) * | 2007-05-18 | 2008-11-19 | 普力摩尔斯奈特株式会社 | Polyacrylate-based polymer |
| CN103922836A (en) * | 2014-03-21 | 2014-07-16 | 成都新柯力化工科技有限公司 | Water soluble fertilizer dissolving promoter and its preparation method |
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