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CN112011090A - Borate internal-addition interface binding agent for PO (polyolefin) membrane and modifier of external coating liquid - Google Patents

Borate internal-addition interface binding agent for PO (polyolefin) membrane and modifier of external coating liquid Download PDF

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Publication number
CN112011090A
CN112011090A CN202010937834.0A CN202010937834A CN112011090A CN 112011090 A CN112011090 A CN 112011090A CN 202010937834 A CN202010937834 A CN 202010937834A CN 112011090 A CN112011090 A CN 112011090A
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coating liquid
film
modified
modifier
borate
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王源理
赵伟萍
许化峰
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Yantai Rongsheng New Material Co ltd
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Yantai Rongsheng New Material Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/55Boron-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/63Additives non-macromolecular organic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04Homopolymers or copolymers of ethene
    • C08J2323/06Polyethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention provides a borate internal-addition interface binding agent and a modifier of an external coating liquid, belongs to the field of fine chemicals, and can solve the problems that the conventional PO film is not friction-resistant, the PO coating liquid is easy to peel and the like. The borate interfacial binding agent and the external coating liquid modifier have the following structural general formula (A):
Figure 169735DEST_PATH_IMAGE001
formula (A) thereofIn, R1Is a straight chain hydrocarbon group of more than 18 carbons; r2Is a hydrocarbon group containing ether bond with carbon chain length of 8-12; r3Is a hydrocarbon group containing an alcohol amine group. Internally added interfacial bonding agent (A)1) And an external coating liquid modifier (A)2) The molecular structures of (A) and (B) are similar, and both have long-acting dripping function. The difference lies in that A1Has a low HLB value (8-10), and A2Has a high HLB value (11-14) to make it emulsify well and have good compatibility with PO coating stock solution. The borate interface binding agent and the external coating liquid modifier provided by the invention can improve the compatibility and the interface binding force of the coating liquid and a film, and compared with the traditional PO film, the dripping durability of the coating liquid is improved by 1.5-2 times.

Description

Borate internal-addition interface binding agent for PO (polyolefin) membrane and modifier of external coating liquid
Technical Field
The invention belongs to the technical field of fine chemicals, and particularly relates to a borate internal-addition interface binding agent and an external coating liquid modifier.
Background
China is a big agricultural country, and Polyethylene (PE) greenhouse films used in agricultural production have a dripping effect, so that fog drops are prevented from being attached to the surface of the greenhouse film to influence light transmittance, meanwhile, the water drops are prevented from dripping on crops to cause the crops to mildew and rot, and the yield is reduced.
The polyethylene dripping film is mainly classified into an internal addition method and an external coating method according to the processing technology. The internal addition method is not effective because the dripping agent is easy to precipitate and migrate from the interior of the greenhouse film and is continuously washed by rain. Theoretically, the dripping agent prepared by the coating method has a dripping lasting period of more than one year, even the dripping lasting period is synchronous with the service life of the greenhouse film, but the defects of small adhesive force between the greenhouse film and the dripping agent, friction resistance of the PO film and the like exist, so that the service life of the PO film is shortened. At present, the coating type dripping agent mainly comprises inorganic latex, a high molecular surfactant, a composite surfactant and the like. The problems of poor adhesion between the coating liquid and the greenhouse film and the like can be solved by adopting methods such as surface modification and the like. In the prior art, no previous work has been reported in the literature for borate-based adjuvants to improve the adhesion of PO coating fluids.
Disclosure of Invention
The invention provides a borate internal-addition interface binding agent and a modifier of an external coating liquid. The molecular structure of the obtained functional additive is characterized in that a boron atom is taken as a central atom, the functional additive is a novel polyol borate surfactant, the compatibility and the interface bonding force of the PO coating liquid and a film can be improved, and the dripping durability of the functional additive can be improved by 1.5-2 times compared with that of the traditional PO film.
In order to achieve the above object, the present invention provides a borate-based interfacial bonding agent and an overcoat liquid modification aid, which are independently developed by the inventors, and have the following structural general formula (a):
Figure 398551DEST_PATH_IMAGE001
formula (A)
Wherein R is1Is greater than 18 carbonsA chain hydrocarbon group; r2Is a hydrocarbon group containing ether bond with carbon chain length of 8-12; r3Is a hydrocarbon group containing an alcohol amine group. Internally added interfacial bonding agent (A)1) And an external coating liquid modifier (A)2) The molecular structures of (A) and (B) are similar, and both have long-acting dripping function. The difference lies in that A1Has a low HLB value (8-10), and A2Has a high HLB value (11-14) to make it emulsify well and have good compatibility with PO coating stock solution.
The optimal dosage proportion of the internal addition interface binding agent in the greenhouse film is 0.2-0.6%.
The invention also provides a modified PO emulsion obtained by emulsification by using the modified auxiliary agent in the technical scheme, and the emulsification process comprises the following steps:
the emulsifying temperature of the deionized water is 50-90 ℃, the rotating speed of an emulsifying machine is 1w-3 w/min, 0.5-5% of PO modification auxiliary agent A is firstly added, the mixture is stirred for 1-10min until the mixture is completely uniform, 5-9.5% of PO modification auxiliary agent B is then added, the mixture is stirred for 1-10min until the mixture is completely uniform, and the mixture is stopped, thus obtaining the modified PO emulsion. And adding the modified PO emulsion into the PO stock solution in proportion, and diluting to obtain the modified PO coating solution.
The polyethylene greenhouse film prepared by the internal addition interface binding agent or the external coating modified PO emulsion obtained by the technical scheme has the dripping long effective period of more than 50 days on a constant-temperature water bath at 60 ℃ under the condition that the height of the water surface to the film is 5 cm.
Compared with the prior art, the invention has the advantages and positive effects that:
1. the borate internal addition interface binding agent takes a boron atom as a central atom, and hydrophilic functional groups such as unsaturated double bonds, carboxyl, hydroxyl and the like are connected to basic borate molecules, so that the borate internal addition interface binding agent not only has a dripping effect, but also has the characteristics of hydrophilic, lipophilic and amphiphilic, and becomes a novel amphiphilic interface active agent, the HLB value of the amphiphilic interface active agent is between 8 and 10, and the molecular weight of the amphiphilic interface active agent is 600-900. After the interface binding agent is added into a PE film, lipophilic groups are tightly combined with the PE, and the hydrophilic groups have good compatibility with functional groups and inorganic particles in PO coating liquid, so that the binding force of two phases is improved, and the problems that the PO film is not friction-resistant, not folding-resistant and the like are solved;
2. the modified PO emulsion prepared by the external coating liquid modifier has amphiphilic characteristics, wherein the HLB value is 11-14, and the modified PO emulsion can be fully emulsified when being added into PO stock solution, on one hand, hydrophilic groups are tightly combined with inorganic components such as silica sol and aluminum sol, and on the other hand, lipophilic groups are combined with PE base materials, so that the compatibility of two phases is improved, the PO coating liquid is more firmly attached, and the service life of a PO film is prolonged.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
And (3) adding 2% of PO modified auxiliary agent A at the emulsification temperature of 50 ℃ and the rotation speed of an emulsifying machine of 1 w/min, stirring for 5min until the mixture is completely uniform, adding 9% of PO modified auxiliary agent B, and stirring for 10min until the mixture is completely uniform, and stopping stirring to obtain the modified PO emulsion. And adding the modified PO emulsion into the PO stock solution in proportion, and diluting to obtain the modified PO coating solution.
Example 2
The emulsifying temperature of the deionized water is 70 ℃, the rotating speed of an emulsifying machine is 1.5 w/min, 0.5 percent of PO modification auxiliary agent A is firstly added, the mixture is stirred for 2min until the mixture is completely uniform, 9.5 percent of PO modification auxiliary agent B is then added, the mixture is stirred for 5min until the mixture is completely uniform, and the mixture is stopped, thus obtaining the modified PO emulsion. And adding the modified PO emulsion into the PO stock solution in proportion, and diluting to obtain the modified PO coating solution.
Example 3
And (3) emulsifying the deionized water at the temperature of 90 ℃ at the rotating speed of the emulsifying machine of 3 w/min, adding 4% of PO modified auxiliary agent A, stirring for 6min until the mixture is completely uniform, adding 6% of PO modified auxiliary agent B, stirring for 10min until the mixture is completely uniform, and stopping stirring to obtain the modified PO emulsion. And adding the modified PO emulsion into the PO stock solution in proportion, and diluting to obtain the modified PO coating solution.
Evaluation of drip Performance test
Internally added interfacial bonding agent test
Experiment one
The internal addition interface bonding agent obtained by the invention is added into a polyethylene greenhouse film, and the dripping performance of the greenhouse film is tested. The results are shown in table 1 below;
TABLE 1 evaluation table for shed film dripping performance
1 2 3 A B
Transmittance (a) 92.37 92.53 91.96 91.93 92.22
Haze/% 12.14 11.73 12.63 13.86 14.03
Initial drop time/s 187 181 184 196 191
Long term of validity/d 52 59 55 33 35
Note: 1-3# are films prepared by the interface bonding agent of the invention respectively; A. b is a general type commercially available PO dripping film;
as can be seen from Table 1, the light transmittance of the 5 samples is not very different, but the haze is reduced after the internal interface bonding agent is added, wherein the haze of No. 2 is the lowest; and the initial dropping time and the long-acting property of the first three groups of formulas added with the interfacial bonding agent are obviously superior to those of the general PO membranes sold in the market, and particularly the long-acting property of No. 2 has the best effect. In conclusion, the 2# membrane in the embodiment of the invention has the best overall effect, can ensure that the haze of the membrane is reduced, the initial dropping time is shortened, the long-acting property of the membrane is improved, and the service life of the PO membrane is prolonged.
Experiment two
Rubbing the 5 groups of new films with a rubbing machine for 50 times, testing in 60 ℃ water bath, and performing a film rubbing resistance test with the results shown in the following table 2;
TABLE 2 evaluation table of film dripping performance
1 2 3 A B
Time to develop Water marks/h 4 5 4.5 1.5 1.5
As can be seen from Table 2, the water mark time of the first 3 samples is obviously longer than that of the general PO film sold in the market, which shows that after the borate type internal addition interface bonding agent is added, the problem that the PO film is not friction-resistant is obviously improved, the bonding force between the greenhouse film and the PO coating liquid is improved, and the service life of the PO film is prolonged.
Coating liquid modifier test
Experiment three
The modified PO emulsions obtained according to the above examples 1-3# as the coating liquid were added to the PO coating liquid to prepare a polyethylene PO film, and the film dripping property test was conducted. The results are shown in table 1 below;
TABLE 1 evaluation table for shed film dripping performance
1 2 3 A B
Transmittance (a) 91.98 92.48 92.11 92.01 92.18
Haze/% 12.26 11.61 11.99 13.22 13.75
Initial drop time/s 184 179 188 189 191
Long term of validity/d 55 60 57 32 35
Note: 1-3# are films prepared according to the modified PO emulsions of examples 1-3, respectively, of the present invention; A. b is a general type commercially available PO dripping film;
as can be seen from Table 1, the transmittance of 5 samples is not very different, but the haze is reduced after the modified PO emulsion is added, wherein the haze of No. 2 is the lowest; the initial dropping time and the long-acting property of the first three groups of formulas added with the modified PO emulsion are obviously superior to those of the general PO membranes sold in the market, and particularly the long-acting property of No. 2 has the best effect. In conclusion, the 2# membrane in the embodiment of the invention has the best overall effect, can ensure that the haze of the membrane is reduced, the initial dropping time is shortened, the long-acting property of the membrane is improved, and the service life of the PO membrane is prolonged.
Experiment four
Rubbing the 5 groups of new films with a rubbing machine for 50 times, testing in 60 ℃ water bath, and performing a film rubbing resistance test with the results shown in the following table 2;
TABLE 2 evaluation table of film dripping performance
1 2 3 A B
Time to develop Water marks/h 5 5.5 5 1.5 2
As can be seen from Table 2, the water mark time of the first 3 samples is obviously longer than that of the common PO film sold in the market, which indicates that the modified PO emulsion of the invention is added into the PO coating liquid, the problem that the PO film is not friction-resistant is obviously improved, the binding force of the greenhouse film and the PO coating liquid is improved, and the service life of the PO film is prolonged.
Test for using internal interface binding agent and external coating liquid modifier simultaneously
The internal addition interface binding agent obtained by the invention and the modified PO emulsion prepared by using the external coating liquid modifier are simultaneously added into the polyethylene greenhouse film in an internal addition and external coating mode, and the dripping performance of the greenhouse film is tested. The results are shown in table 1 below.
Experiment five
TABLE 1 evaluation table for shed film dripping performance
1 2 3 A B
Transmittance (a) 92.20 92.84 91.97 91.89 92.25
Haze/% 11.20 10.56 11.34 13.05 12.88
Initial drop time/s 175 168 169 185 180
Long term of validity/d 59 65 60 32.5 34
Note: 1-3# are films prepared by the interface binding agent and the modified PO emulsion respectively; A. b is a general type commercially available PO drip membrane.
As can be seen from Table 1, the transmittance of the 5 samples is not very different, but the haze is reduced after the interfacial bonding agent and the modified PO emulsion are added, wherein the haze of No. 2 is the lowest; and the initial dropping time and the long-acting property of the first three groups of formulas added with the internal interface binding agent and the modified PO emulsion are obviously superior to those of the general PO membranes sold in the market, and particularly the long-acting property of No. 2 has the best effect. In conclusion, the 2# membrane in the embodiment of the invention has the best overall effect, can ensure that the haze of the membrane is reduced, the initial dropping time is shortened, the long-acting property of the membrane is improved, and the service life of the PO membrane is prolonged.
Compared with the first four experiments, the two experiments have the advantages of lower formula haze value, shortened initial dropping time and prolonged long-term period. It shows that the effect of using both the two is better.
Experiment six
Rubbing the 5 groups of new films with a rubbing machine for 50 times, testing in 60 ℃ water bath, and performing a film rubbing resistance test with the results shown in the following table 2;
TABLE 2 evaluation table of film dripping performance
1 2 3 A B
Time to develop Water marks/h 6 7 7 2 1.5
As can be seen from Table 2, the water mark time of the first 3 samples is obviously longer than that of the general PO film sold in the market, which shows that after the interface binding agent and the modified PO emulsion of the invention are added, the problem that the PO film is not friction-resistant is obviously improved, the binding force of the greenhouse film and the PO coating liquid is improved, and the service life of the PO film is prolonged.
Meanwhile, compared with the first four groups of experiments, the time of water marks on the formulas used for the two groups of experiments is obviously prolonged, which shows that the effect of the two groups of experiments is better when the two groups of experiments are used simultaneously.

Claims (6)

1. The modifier of the borate internal-addition interface binding agent and the external coating liquid has the following structural general formula (A):
Figure 469915DEST_PATH_IMAGE001
formula (A)
Wherein R is1Is a straight chain hydrocarbon group of more than 18 carbons; r2Is a hydrocarbon group containing ether bond with carbon chain length of 8-12; r3Is a hydrocarbon group containing an alcohol amine group, and an internal interfacial bonding agent (A)1) And an external coating liquid modifier (A)2) The molecular structures of the two have similar structures, and both have long-acting dripping function, the difference is that A1Has a low HLB value (8-10), and A2Has a high HLB value (11-14) to make it emulsify well and have good compatibility with PO coating stock solution.
2. The internal interface bonding agent according to claim 1, wherein the optimal amount of the internal interface bonding agent in the greenhouse film is 0.2-0.6%.
3. The emulsification process of the topcoat modifier of claim 1 to obtain a modified PO emulsion comprising the steps of:
the method comprises the steps of firstly adding 0.5-5% of PO modification auxiliary agent A into deionized water at the emulsification temperature of 50-90 ℃ and the rotation speed of an emulsifying machine of 1w-3 w/min, stirring for 1-10min till the mixture is completely uniform, then adding 5-9.5% of PO modification auxiliary agent B into the mixture, stirring for 1-10min till the mixture is completely uniform, and then stopping stirring to obtain modified PO emulsion, adding the modified PO emulsion into PO stock solution in proportion, and then diluting to obtain the modified PO coating solution.
4. A greenhouse film prepared by using the interfacial bonding agent of claim 1, 2 or 3 and a modified PO emulsion.
5. The greenhouse film of claim 2, wherein the greenhouse film has a drip-growth period of more than 50 days on a thermostatic water bath at 60 ℃ under the condition that the height of the water surface from the film is 5 cm.
6. Use of the interfacial bonding agent and the modified PO emulsion according to claim 1, 2 or 3 in the preparation of greenhouse films.
CN202010937834.0A 2020-09-09 2020-09-09 Borate internal-addition interface binding agent for PO (polyolefin) membrane and modifier of external coating liquid Pending CN112011090A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112916795A (en) * 2021-01-15 2021-06-08 西安合力汽车配件有限公司 Water-soluble release agent
CN117659777A (en) * 2023-11-10 2024-03-08 杭州扬子新材料科技有限公司 Coating liquid for PO film and preparation process thereof

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JP2009184988A (en) * 2008-02-07 2009-08-20 Institute Of Physical & Chemical Research Novel boron compound and intracellular calcium concentration regulator or pharmaceutical composition containing the same
US20110212919A1 (en) * 2008-08-11 2011-09-01 Japan Science And Technology Agency Protein cross-linking inhibitor
CN103387692A (en) * 2012-05-11 2013-11-13 天津博克尼科技发展有限公司 Method for utilizing complex formulation of waste oil surfactants to prepare agricultural film anti-dropping agent
CN106188980A (en) * 2016-08-25 2016-12-07 江阴市富华包装材料有限公司 A kind of clear flexible PVC film and preparation method thereof
CN111068577A (en) * 2019-12-18 2020-04-28 烟台融晟新材料有限公司 Boric acid ester drip agent, preparation method thereof and greenhouse film prepared by same

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Publication number Priority date Publication date Assignee Title
JPH10120790A (en) * 1996-10-15 1998-05-12 Kawamura Inst Of Chem Res Self-organizing membrane, self-organizing polymeric thin membrane and organosilicon compound
CN101029151A (en) * 2007-04-02 2007-09-05 广东华南精细化工研究院有限公司 Boron antistatic agent for polyolefine coated film, its production and use
JP2009184988A (en) * 2008-02-07 2009-08-20 Institute Of Physical & Chemical Research Novel boron compound and intracellular calcium concentration regulator or pharmaceutical composition containing the same
US20110212919A1 (en) * 2008-08-11 2011-09-01 Japan Science And Technology Agency Protein cross-linking inhibitor
CN103387692A (en) * 2012-05-11 2013-11-13 天津博克尼科技发展有限公司 Method for utilizing complex formulation of waste oil surfactants to prepare agricultural film anti-dropping agent
CN106188980A (en) * 2016-08-25 2016-12-07 江阴市富华包装材料有限公司 A kind of clear flexible PVC film and preparation method thereof
CN111068577A (en) * 2019-12-18 2020-04-28 烟台融晟新材料有限公司 Boric acid ester drip agent, preparation method thereof and greenhouse film prepared by same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112916795A (en) * 2021-01-15 2021-06-08 西安合力汽车配件有限公司 Water-soluble release agent
CN117659777A (en) * 2023-11-10 2024-03-08 杭州扬子新材料科技有限公司 Coating liquid for PO film and preparation process thereof

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