CN107011475A - A kind of GSZ latex and preparation method thereof - Google Patents
A kind of GSZ latex and preparation method thereof Download PDFInfo
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- CN107011475A CN107011475A CN201710261676.XA CN201710261676A CN107011475A CN 107011475 A CN107011475 A CN 107011475A CN 201710261676 A CN201710261676 A CN 201710261676A CN 107011475 A CN107011475 A CN 107011475A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
- D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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Abstract
The invention discloses a kind of GSZ latex and preparation method thereof, the preparation method of the styrene-acrylic latex comprises the following steps：The aqueous solution of the mixture of carboxylic acid monomer, (methyl) acrylate monomer, (methyl) styrene monomer, cross-linking monomer, sodium metasilicate, emulsifying agent and initiator is subjected to free-radical emulsion polymerization, the reaction time is 3~10 hours at 60 DEG C~90 DEG C, reaction product is adjusted into pH=6~9 with alkaline matter, through being filtrated to get latex.GSZ latex made from the inventive method, hence it is evident that improve the constancy and intensity of GSZ, meets high-performance in GSZ production process, environmental requirement.
Description
Technical field
Shaping glue field is used the present invention relates to a kind of GSZ, and in particular to a kind of GSZ latex and its preparation
Method.
Background technology
Emulsion is used in GSZ, and the main function risen is sizing and enhancing.Constituted in the market according to raw material
Difference mainly has the types such as styrene-butadiene emulsion, styrene-acrylic latex, pure-acrylic emulsion.
Styrene-butadiene emulsion, i.e., the usual SB latex, is one kind of synthetic emulsion, is based on styrene, divinylic monomer
Want Material synthesis.Styrene-acrylic latex, i.e., the usual SA emulsions, are using styrene, acrylic acid or acrylate as primary raw material
Synthesis.Pure-acrylic emulsion, is using styrene, acrylic acid or acrylate as main Material synthesis.According to different geotechnological lattice
The requirement of grid processing, the different monomer composition by adjusting synthesizes different types of emulsion.Enhancing building is primarily served after use
The intensity of grid, prevents the effect of GSZ deformation.
Chinese patent CN105153565A discloses a kind of alkali-proof glass fiber mesh dip-coating high-intensity high-tenacity ring
Oxygen tree fat modifying cinepazid latex and preparation method thereof, certain determines applied in the production of GSZ, also having to GSZ
Type is acted on, but intensity improves little, and civil grille is partially soft.
The content of the invention
The present invention proposes a kind of GSZ latex and preparation method thereof to solve above mentioned problem of the prior art,
The GSZ latex of the present invention is applied to make GSZ have more preferable constancy and intensity in the production of GSZ.
To achieve the above object, the present invention uses following technical scheme：
The first aspect of the invention is to provide a kind of preparation method of GSZ latex, the system of the styrene-acrylic latex
Preparation Method comprises the following steps：By carboxylic acid monomer, (methyl) acrylate monomer, (methyl) styrene monomer, cross-linking monomer, silicon
The aqueous solution of the mixture of sour sodium, emulsifying agent and initiator carries out free radical emulsion copolymerization, after 3~10 hours reaction time, will
Reaction product is adjusted with alkaline matter to pH=6~9, after filtering, the GSZ latex is made.
Further, in the preparation method of the GSZ latex, each component and parts by weight in reaction system
It is as follows：
It is further preferred that in the preparation method of the GSZ latex, each component and weight in reaction system
Number is as follows：
Further, in the preparation method of the GSZ latex, the carboxylic acid monomer is selected from acrylic acid, methyl
At least one of acrylic acid, maleic acid, fumaric acid, itaconic acid.
Further, in the preparation method of the GSZ latex, (methyl) acrylate is selected from propylene
Nitrile, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid-2-ethyl caproite, metering system
Sour methyl esters, EMA, n-BMA, methacrylic acid -2- ethylhexyls, acrylic acid, metering system
At least one of sour C8~C16 Arrcostabs；
It is further preferred that in the preparation method of the GSZ latex, (methyl) acrylate is preferred
For n-butyl acrylate, methyl methacrylate or acrylic acid-2-ethyl caproite.
Further, in the preparation method of the GSZ latex, the emulsifying agent is selected from pi-allyl polyoxy second
At least one of alkene ether ammonium sulfate, allyl polyethenoxy ether, vinyl APEO.
Further, in the preparation method of the GSZ latex, the cross-linking monomer be selected from divinylbenzene,
At least one of hydroxypropyl acrylate, hydroxy-ethyl acrylate.
Further, in the preparation method of the GSZ latex, the initiator is selected from potassium peroxydisulfate, over cure
At least one of sour sodium, ammonium persulfate.
Further, in the preparation method of the GSZ latex, the alkaline matter is selected from the hydrogen of alkali metal
Oxide, preferably sodium hydroxide.
Further, in the preparation method of the GSZ latex, the reaction temperature of radical polymerization is 60 DEG C
~90 DEG C.
It is further preferred that in the preparation method of the GSZ latex, the reaction temperature of radical polymerization is
70 DEG C~75 DEG C.
The second aspect of the invention is to provide GSZ latex prepared by a kind of use above method.
Further, in described GSZ latex, the weight solid content of latex is 20%~40%.
It is further preferred that in described GSZ latex, the weight solid content of latex is 30%~35%.
It is further preferred that in described GSZ latex, the reaction time is 4~6 hours；Reaction product
Adjusted with alkaline matter to pH=6~6.5.
The third aspect of the invention is to provide a kind of application of described GSZ latex, and it is used for GSZ
In impregnation composition in production process.
The inventors discovered that in GSZ of the invention with a small amount of cross-linking monomer and sodium metasilicate is added in latex, exceeding meaning
Material, applied in GSZ impregnation composition, the intensity of GSZ increases；Its reason is analyzed, this is due to silicon
Sour sodium has the composition of silicon with GSZ yarn, the effect with similar compatibility, during high temperature drying, plays crane span structure and makees
With；The cross-linking monomer in latex makes latex be in thermosetting in latex drying process simultaneously, and enhancing is viscous with GSZ yarn
Knotting strength, while be able to can be reacted with the active group of some in pitch, external manifestation is the GSZ using the present invention
The intensity of GSZ can be significantly improved with latex.
The present invention uses above-mentioned technical proposal, compared with prior art, have the following technical effect that：
GSZ provided by the present invention is a kind of high-performance that can meet GSZ production, environmentally friendly production with latex
Product；The product is used in the production of GSZ, can significantly improve the constancy and intensity of GSZ；Moreover, the geotechnique
Grid is simple and convenient to operate with the preparation method of latex, production cost is low.
Embodiment
The present invention is described in more detail below by specific embodiment, for a better understanding of the present invention,
But following embodiments are not intended to limit the scope of the invention.
The preparation of the GSZ latex of embodiment 1：
0.5 gram of allyl polyethenoxy ether ammonium sulfate, 0.5 gram of potassium peroxydisulfate and 153.3 are added in 2000ml reactors
Gram distilled water, is completely dissolved into the aqueous solution, is stirred heating, is heated to temperature 60 C, carries out polymerisation；Then it is added dropwise to
100 grams of styrene, 0.5 gram of mix monomer of divinylbenzene, time for adding 6 hours；1 gram of sodium metasilicate is added, continues to stir mixed
Close 4 hours, be cooled to 25 DEG C, through 100 mesh sieve net filtrations, obtain GSZ latex, solid content 39.87wt%, pH=
6.21 (being measured using PHS-3C Accurate pHs).
The preparation of the GSZ latex of embodiment 2：
2 grams of allyl polyethenoxy ether ammonium sulfate, 3 grams of vinyl APEOs, 5 grams are added in 2000ml reactors
Sodium peroxydisulfate and 1300.5 grams of distilled water, are completely dissolved into the aqueous solution, are stirred heating, and 90 DEG C of heating-up temperature is polymerize
Reaction；Then 2 grams of 100 grams of methyl styrene, 5 grams of methacrylic acid, 200 grams of ethyl acrylate and hydroxy-ethyl acrylate are added dropwise to
Mix monomer, time for adding 2 hours；5 grams of sodium metasilicate are added, continues to stir mixing 1 hour, 25 DEG C is cooled to, with 12.5 grams
40wt% sodium hydrate aqueous solutions are neutralized, through 100 mesh sieve net filtrations, obtain GSZ latex, solid content 20.17wt%,
PH=8.88 (is measured) using PHS-3C Accurate pHs.
The preparation of the GSZ latex of embodiment 3：
3 grams of allyl polyethenoxy ethers, 2 grams of ammonium persulfates, 1 gram of itaconic acid and 494.67 are added in 2000ml reactors
Gram distilled water, is completely dissolved into the aqueous solution, is stirred heating, and 80 DEG C of heating-up temperature carries out polymerisation；Then it is added dropwise to benzene
50 grams of ethene, 50 grams of methyl styrene, 2 grams of acrylic acid, 100 grams of n-BMA, 0.5 gram of hydroxypropyl acrylate, two
0.5 gram of mix monomer of vinyl benzene, time for adding 4 hours；3 grams of sodium metasilicate are added, continues to stir mixing 1 hour, is cooled to
25 DEG C, neutralized with 10 grams of 30wt% sodium hydrate aqueous solutions, through 100 mesh sieve net filtrations, obtain GSZ latex, solid content
30.23wt%, pH=8.13 (are measured) using PHS-3C Accurate pHs.
The preparation of the GSZ latex of embodiment 4：
Added in 2000ml reactors 1 gram of allyl polyethenoxy ether, 1 gram of allyl polyethenoxy ether ammonium sulfate, 2 grams
Ammonium persulfate and 1 gram of sodium peroxydisulfate, 1 gram of fumaric acid, 1 gram of maleic acid and 292.49 grams of distilled water, are completely dissolved into the aqueous solution；Enter
Row agitating and heating, 70 DEG C of heating-up temperature carries out polymerisation；Then 20 grams of styrene, 80 grams of methyl styrene, propylene are added dropwise to
50 grams of acid -2- ethylhexyls and 0.8 gram of mix monomer of divinylbenzene, time for adding 3 hours add 2 grams of sodium metasilicate, continue
Stirring mixing 1 hour, is cooled to 25 DEG C, is neutralized, through 100 mesh sieve net filtrations, obtained with 10 grams of 20wt% sodium hydrate aqueous solutions
GSZ latex, solid content 35.1wt%, pH=7.45 (are measured) using PHS-3C Accurate pHs.
The preparation of the GSZ latex of embodiment 5：
In 2000ml reactors add 4 grams of allyl polyethenoxy ether ammonium sulfate, 2 grams of ammonium persulfates, 1 gram of fumaric acid and
789 grams of distilled water, are completely dissolved into the aqueous solution, are stirred heating, and 75 DEG C of heating-up temperature carries out polymerisation；Then it is added dropwise
Enter 100 grams of styrene, 150 grams of methyl methacrylate, 3 grams of mix monomers of 1.5 grams of hydroxypropyl acrylate and acrylic acid, during dropwise addition
Between 5 hours；4 grams of sodium metasilicate are added, continues to stir mixing 1 hour, is cooled to 25 DEG C, it is water-soluble with 10 grams of 25wt% sodium hydroxides
Liquid is neutralized, and through 100 mesh sieve net filtrations, obtains GSZ latex, solid content 25.25wt%, pH=6.95 (use PHS-3C
Accurate pH is measured).
Comparative example：The styrene-acrylic latex prepared by CN105153565A method
With embodiment 1~5 and comparative example, operated by following techniques：
A, embodiment 1~5 and comparative example be diluted to weight solid content 20%, by styrene-acrylic latex：Emulsified asphalt (city
Sell, weight solid content 30%)=2：5 are hybridly prepared into dipping solution
B, the GSZ single yarn of non-impregnation is soaked in each dipping solution, according to soak time 2min, impregnation resin content
18% or so, after being dried up using hair-dryer, it is placed in 150 DEG C of baking ovens and dries 10min.
The feel soft durometer of GSZ yarn after C, observation impregnation, and detect single yarn Strength Changes after impregnation.
Criterion：Intensity shows that more greatly the enhancing effect of GSZ latex is better
| Intensity/N | |
| Non- impregnation | 105 |
| Comparative example | 205 |
| Embodiment 1 | 255 |
| Embodiment 2 | 263 |
| Embodiment 3 | 248 |
| Embodiment 4 | 243 |
| Embodiment 5 | 254 |
It can be seen that from above-mentioned application result：The GSZ latex prepared using the embodiment of the present invention 1~5, it is and right
Ratio is compared, and to GSZ enhancing effect more preferably, can significantly improve the constancy and intensity of GSZ.
The specific embodiment of the present invention is described in detail above, but it is intended only as example, and the present invention is not limited
It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and
Substitute also all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and
Modification, all should be contained within the scope of the invention.
Claims (9)
1. a kind of preparation method of GSZ latex, it is characterised in that the preparation method of the styrene-acrylic latex includes following
Step：By carboxylic acid monomer, (methyl) acrylate monomer, (methyl) styrene monomer, cross-linking monomer, sodium metasilicate, emulsifying agent and
The aqueous solution of the mixture of initiator carries out free radical emulsion copolymerization, after 3~10 hours reaction time, by reaction product alkalescence
Material is adjusted to pH=6~9, after filtering, the GSZ latex is made.
2. the preparation method of GSZ latex according to claim 1, it is characterised in that in reaction system each component and
Parts by weight are as follows：
3. the preparation method of GSZ latex according to claim 1 or claim 2, it is characterised in that carboxylic acid monomer's choosing
From at least one of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid；(methyl) acrylate is selected from third
Alkene nitrile, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid-2-ethyl caproite, methyl-prop
E pioic acid methyl ester, EMA, n-BMA, methacrylic acid -2- ethylhexyls, acrylic acid, methyl-prop
At least one of olefin(e) acid C8~C16 Arrcostabs.
4. the preparation method of GSZ latex according to claim 1 or claim 2, it is characterised in that the emulsifying agent is selected from
At least one of allyl polyethenoxy ether ammonium sulfate, allyl polyethenoxy ether, vinyl APEO；The crosslinking
Monomer is selected from least one of divinylbenzene, hydroxypropyl acrylate, hydroxy-ethyl acrylate.
5. the preparation method of GSZ latex according to claim 1 or claim 2, it is characterised in that the initiator is selected from
At least one of potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate；The alkaline matter is selected from the hydroxide of alkali metal.
6. the preparation method of GSZ latex according to claims 1 to 2, it is characterised in that radical polymerization
Reaction temperature is 60 DEG C~90 DEG C.
7. a kind of GSZ latex prepared such as any one of claim 1~6 methods described.
8. GSZ latex according to claim 7, it is characterised in that the weight solid content of latex is 20%~
40%.
9. a kind of application of GSZ latex as claimed in claim 7 or 8, it is characterised in that for GSZ life
In impregnation composition during production.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109957068A (en) * | 2017-12-14 | 2019-07-02 | 东升新材料（山东）有限公司 | A kind of U.S. line paper carboxylic styrene butadiene latex and its preparation method and application |
| CN109957074A (en) * | 2017-12-14 | 2019-07-02 | 东升新材料（山东）有限公司 | A kind of preparation method and applications of wallpaper carboxylic styrene butadiene latex |
| CN109957069A (en) * | 2017-12-14 | 2019-07-02 | 东升新材料（山东）有限公司 | A kind of preparation method and applications of U.S. line paper carboxylic styrene butadiene latex |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109957068A (en) * | 2017-12-14 | 2019-07-02 | 东升新材料（山东）有限公司 | A kind of U.S. line paper carboxylic styrene butadiene latex and its preparation method and application |
| CN109957074A (en) * | 2017-12-14 | 2019-07-02 | 东升新材料（山东）有限公司 | A kind of preparation method and applications of wallpaper carboxylic styrene butadiene latex |
| CN109957069A (en) * | 2017-12-14 | 2019-07-02 | 东升新材料（山东）有限公司 | A kind of preparation method and applications of U.S. line paper carboxylic styrene butadiene latex |
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Application publication date: 20170804 |