CN107177341B - A kind of Nano-meter SiO_22The preparation method of the aqueous adhesive of modified polyvinylalcohol - Google Patents
A kind of Nano-meter SiO_22The preparation method of the aqueous adhesive of modified polyvinylalcohol Download PDFInfo
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- CN107177341B CN107177341B CN201710315934.8A CN201710315934A CN107177341B CN 107177341 B CN107177341 B CN 107177341B CN 201710315934 A CN201710315934 A CN 201710315934A CN 107177341 B CN107177341 B CN 107177341B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
- C08G18/3895—Inorganic compounds, e.g. aqueous alkalimetalsilicate solutions; Organic derivatives thereof containing no direct silicon-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6212—Polymers of alkenylalcohols; Acetals thereof; Oxyalkylation products thereof
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a kind of Nano-meter SiO_2s2The preparation method of Modified Polyvinyl Alcohol Based Waterborne Water adhesive, this method pass through aminosilane coupling agent modifying Si02, then with isocyanates cross linking modified PVA macromolecular chain simultaneously, to enhance the water resistance of PVA.The present invention provides new thinking for the research of novel environment friendly wood adhesive, having preferable adhesive strength (3.1-3.6MPA) and water resistance using modified polyvinylalcohol adhesive made from the method for the present invention, (time of coming unglued greater than 36h), can replace acetals adhesive in part occasion.
Description
Technical field
The present invention relates to field of adhesive technology, and in particular to a kind of Nano-meter SiO_22Modified Polyvinyl Alcohol Based Waterborne Water adhesive
Preparation method.
Background technique
Polyvinyl alcohol (PVA) is a kind of polyhydric high-molecular compound, can be dissolved in hot water, dense glue is to timber, paper
, fiber, cement, ceramic polar materials there is stronger bonding force, but the intensity and water resistance of PVA glue film itself
Difference is restricted its application range.
People, which often add formaldehyde, butyraldehyde or crotonaldehyde, makes PVA acetalation, to improve its water solubility, but acetals adhesive
Middle remaining free formaldehyde can generate baneful influence to human health and environment.Xia Chidan et al. is with micro isocyanate-modified
PVA has been made one-component white latex, test result show the water resistance of the latex and bond properties increase and
Unharmful substance release, this studies the application range for extending PVA adhesive.(Xia Chidan, Yu Hannian, Zhou Libin.Toluene two
The research of isocyanates and water based polyethylene alcohol adhesive cross-linking reaction.Chemistry and bonding, 2001,5,197-199.) a small amount of ring
The addition of oxygen resin and waterglass can also significantly improve the bonding strength and water resistance of PVA glue, as Liu Xiaomei et al. is reported
's.(Xiaomei Liu.PVA Wood Adhesive Modified with Sodium Silicate Cross-linked
Copolymer.2012 International Conference on Biobase Material Science and
Engineering (BMSE), 2012,108-111.) Zhang Xinli etc. utilizes starch and borax modified PVA, and it is high, resistance to that intensity has been made
Aqueous glued board PVA/ starch adhesive (Zhang Xinli, Wu Yiqiang, Hu Yunchu that can be good.High strong water resistant PVA/ starch timber glue
The preparation of glutinous agent and performance characterization.Sino-South African Forestry University of Science and Technology's journal, 2012,32 (1), 104-108.).
In recent years, significant progress is achieved with the research that inorganic nano-particle carries out toughening enhancing to polymer, it is more next
More attract people's attention.However, inorganic nano-particle partial size is small, large specific surface area, it each other can be because of huge surface energy
And reunite together, form the biggish offspring of partial size.If this inorganic particulate is directly appended in polymer, not only not
It can play the role of enhancing polymer toughening, the performance of material can instead declined, therefore before using inorganic nano-particle,
It is modified that surface must be carried out to it.(Yuan Qingfeng, Gao Yanmin, Lv Weigang.KH-550 modified Nano Si02To epoxy adhesive performance
Influence chemistry and bonding, 2009,31 (3), 26-28；Li Yuping, Wang Yaqiang, Wei Wei.Nano Si 02Surface grafting and its
Dispersion stabilization in in-situ emulsion polymerization system.Hunan University's journal, 2006,33 (3), 80-83 etc.)
Based on the special result that modified Nano particle plays in the polymer, the present invention passes through aminosilane coupling agent modifying
Si02, then with isocyanates cross linking modified PVA macromolecular chain simultaneously, to enhance the water resistance of PVA.In addition, the present invention is novel
The research of environment protective lumber adhesive provides new thinking, using the method for the present invention products obtained therefrom have preferable adhesive strength and
Water resistance can replace acetals adhesive in part occasion.
Summary of the invention
The purpose of the present invention is to provide a kind of Nano-meter SiO_2s2The preparation method of Modified Polyvinyl Alcohol Based Waterborne Water adhesive, the party
Method is specifically includes the following steps: (a) prepares the hydrolysis of amino silicane coupling agent using organic solvent, amino silicane coupling agent and water
Liquid is then added nano silica and catalyst and is uniformly dispersed into hydrolyzate, and heating is reacted to obtain modified Nano
Silica；(b) polyvinyl alcohol is soluble in water, add emulsifier, catalyst, modified manometer silicon dioxide, isocyanic acid
Ester, up to modified polyvinylalcohol adhesive after being stirred to react.
According to above scheme, the dosage of each substance is calculated as in step (a) with mass fraction: 6-8 parts of organic solvent, amino silicone
1.4-2 parts of alkane coupling agent, 1.4-2 parts of water, 10-15 parts of nano silica, wherein the dosage of catalyst is amino silane coupling
The 1-3wt% of agent dosage.
According to above scheme, the dosage of each substance is calculated as in step (b) with mass fraction: 100 parts of polyvinyl alcohol, water
1100-1400 parts, 3-5 parts of emulsifier, 2.5-3 parts of modified manometer silicon dioxide, 3-6 parts of isocyanates, the wherein use of catalyst
Amount is the 1-3wt% of isocyanates dosage.
According to above scheme, the organic solvent is one of ethyl acetate, acetone, toluene, dimethylbenzene.
According to above scheme, the amino silicane coupling agent is gamma-aminopropyl-triethoxy-silane, phenylaminomethyl front three
One of common amino silicane coupling agents such as oxysilane, N- β (aminoethyl)-γ-aminopropyltriethoxy diethoxy silane.
According to above scheme, the emulsifier is the anion such as OP-10, lauryl sodium sulfate, nekal
One of emulsifier or nonionic emulsifier.
According to above scheme, the isocyanates be toluene di-isocyanate(TDI), hexamethylene diisocyanate, triphenyl methane -4,
One of the diisocyanate or polyisocyanates such as 4 ', 4 "-triisocyanate.
According to above scheme, step (a) and step (b) catalyst are dibutyltin dilaurate.
According to above scheme, 20- need to be stirred at normal temperature when preparing the hydrolyzate of amino silicane coupling agent in step (a)
45min is added after nano silica into hydrolyzate and stirs 20-40min, then ultrasound point with the rate of 4500-6000r/min
10-20min is dissipated, catalyst is subsequently added into and mixed liquor is warming up to 70-90 DEG C of reaction 100-140min.
According to above scheme, when in step (b) with water-soluble Polyvinyl alcohol, first polyvinyl alcohol-aqueous mixtures are heated to
It 60-100 DEG C and stirs until be completely dissolved, is then cooled to room temperature, adds stirring at normal temperature 30-50min after all materials.
Compared with prior art, the invention has the benefit that (1) utilizes Nano-meter SiO_22Chemical bond is formed with polyvinyl alcohol
Connection, using nanosized SiO_2 as physical crosslinking point, water resistance and the adhesive strength for enhancing polyvinyl alcohol adhesive are equal, glued board
Time of coming unglued greater than 36h, bonding strength reaches 3.1MPa to 3.6MPa；(2) one-component that viscosity is 3~10ps has been prepared
Aqueous adhesive, the adhesive are discharged without poisonous and harmful substance, environmental protection, can replace aldehyde-containing type adhesive in part occasion；(3) it makes
Preparation Method is simple, at low cost.
Specific embodiment
To make those of ordinary skill in the art fully understand technical solution of the present invention and beneficial effect, below in conjunction with specific
Embodiment is further detailed, but cited embodiment is not constituted to any restriction of the invention.
The present invention is utilized amino silicane coupling agent to Si02Be modified, then with isocyanates cross linking modified PVA simultaneously
Macromolecular chain, has obtained the modified polyvinylalcohol adhesive with preferable adhesive strength and water resistance, and specific reaction principle is as follows
It is shown:
Step 1: Nano-meter SiO_22Surface amination
Wherein: X is hydrolyzable groups, including OCH3、OC2H5Deng.
Step 2: cross linking modified PVA
Wherein, R ' is alkyl, and R ＂ is
Adhesive strength test: it is tested by 4.15 in standard GB/T/T 17657-1999.
Water resistance test: the glued board after drying being placed in 25 DEG C of thermostatted water and impregnated, and record glue-line disconnection is taken
Between.
Embodiment 1
Step 1: according to mass fraction meter (similarly hereinafter), 6 parts of ethyl acetate of addition, 1.4 parts of water and 1.4 parts into reaction flask
γ-aminopropyl triethoxysilane obtains the hydrolyzate of amino silicane coupling agent after stirring 20min under room temperature；
Step 2: being added 10 parts of nano silicas in Xiang Shangshu hydrolyzate, stirs 35min with the rate of 4500r/min,
Re-ultrasonic dispersion 10min, is subsequently added into dibutyltin dilaurate, and dosage is gamma-aminopropyl-triethoxy-silane dosage
1wt%.Mixed liquor is warming up to 90 DEG C, 100min is to get modified manometer silicon dioxide for reaction, spare；
Step 3: being added 1100 parts of water, 100 parts of polyvinyl alcohol in a kettle, is warming up to 90 DEG C, stirring is until polyethylene
Alcohol all dissolves, then is down to room temperature.Then 3 parts of OP-10 are added into solution, the modified nano-silica that 2.5 parts of steps (2) obtain
SiClx, 3 parts of toluene di-isocyanate(TDI)s and dibutyltin dilaurate, wherein dibutyltin dilaurate dosage is toluene
The 1%wt of diisocyanate dosage.It is stirred to react 30min, is discharged to get modified polyvinylalcohol adhesive.
Water resistance and adhesive strength test result show the time of coming unglued of glued board greater than 36h, and bonding strength reaches
3.5MPa。
Embodiment 2
Step 1: 6 parts of acetone, 1.5 parts of water and 1.7 parts of phenylaminomethyl trimethoxy silanes are added into reaction flask, often
After the lower stirring 30min of temperature, the hydrolyzate of amino silicane coupling agent is obtained；
Step 2: being added 12 parts of nano silicas in Xiang Shangshu hydrolyzate, stirs 30min with the rate of 5000r/min,
Re-ultrasonic dispersion 15min, is subsequently added into dibutyltin dilaurate, and dosage is phenylaminomethyl trimethoxy silane dosage
2wt%.Mixed liquor is warming up to 85 DEG C, 110min is to get modified manometer silicon dioxide for reaction, spare；
Step 3: 1200 parts of water, 100 parts of polyvinyl alcohol being added into reaction kettle, are warming up to 80 DEG C, stirring is until polyethylene
Alcohol all dissolves, then is down to room temperature.Then be added that 3 parts of lauryl sodium sulfate, 2.7 parts of steps (2) obtain into solution changes
Property nano silica, 5 parts of hexamethylene diisocyanates and dibutyltin dilaurate, the dosage of dibutyltin dilaurate
It is the 2wt% of hexamethylene diisocyanate dosage.It is stirred to react 45min, is discharged to get modified polyvinylalcohol adhesive.
Water resistance and adhesive strength test result show the time of coming unglued of glued board greater than 36h, and bonding strength reaches
3.5MPa。
Embodiment 3
Step 1: 7 parts of toluene, 1.6 parts of water and 1.4 parts of N- β (aminoethyl)-γ-aminopropyltriethoxies are added into reaction flask
Diethoxy silane obtains the hydrolyzate of amino silicane coupling agent after stirring 40min under room temperature；
Step 2: being added 15 parts of nano silicas in Xiang Shangshu hydrolyzate, stirs 25min with the rate of 5500r/min,
Re-ultrasonic dispersion 15min, is subsequently added into dibutyltin dilaurate, and dosage is N- β (aminoethyl)-γ-aminopropyltriethoxy
The 3wt% of diethoxy silane dosage.Mixed liquor is warming up to 80 DEG C, 120min is to get modified manometer silicon dioxide for reaction, standby
With；
Step 3: 1300 parts of water, 100 parts of polyvinyl alcohol being added into reaction kettle, are warming up to 70 DEG C, stirring is until polyethylene
Alcohol all dissolves, then is down to room temperature.Then 4 parts of nekals are added into solution, 2.8 parts of step step 2 obtain
Modified manometer silicon dioxide, 5 parts of triphenyl methanes -4,4 ', 4 ＂-triisocyanate and dibutyltin dilaurate, wherein
The dosage of dibutyltin dilaurate is the " 3wt% of-triisocyanate dosage of triphenyl methane -4,4 ', 4.It is stirred to react
40min discharges to get modified polyvinylalcohol adhesive.
Water resistance and adhesive strength test result show the time of coming unglued of glued board greater than 36h, and bonding strength reaches
3.3MPa。
Embodiment 4
Step 1: 8 parts of dimethylbenzene, 2 parts of water and 1.7 parts of Y- aminopropyl triethoxysilanes, room temperature are added into reaction flask
After lower stirring 30min, the hydrolyzate of amino silicane coupling agent is obtained；
Step 2: being added 13 parts of nano silicas in Xiang Shangshu hydrolyzate, stirs 20min with the rate of 6000r/min,
Re-ultrasonic dispersion 10min, is subsequently added into dibutyltin dilaurate, and dosage is Y- aminopropyl triethoxysilane dosage
1wt%.Mixed liquor is warming up to 75 DEG C, 130min is to get modified manometer silicon dioxide for reaction, spare；
Step 3: 1400 parts of water, 100 parts of polyvinyl alcohol being added into reaction kettle, are warming up to 60 DEG C, stirring is until polyethylene
Alcohol all dissolves, then is down to room temperature.3 parts of OP-10 are added into mixed solution, the modified nano-silica that 2.9 parts of steps (2) obtain
SiClx, 6 parts of hexamethylene diisocyanates and dibutyltin dilaurate, wherein the dosage of dibutyltin dilaurate be oneself two
The 1wt% of isocyanates dosage.It is stirred to react 35min, is discharged to get modified polyvinylalcohol adhesive.
Water resistance and adhesive strength test result show the time of coming unglued of glued board greater than 36h, and bonding strength reaches
3.2MPa。
Embodiment 5
Step 1: 8 parts of acetone, 1.8 parts of water and 2 parts of phenylaminomethyl trimethoxy silanes, room temperature are added into reaction flask
After lower stirring 45min, the hydrolyzate of amino silicane coupling agent is obtained；
Step 2: being added 15 parts of nano silicas in Xiang Shangshu hydrolyzate, stirs 40min with the rate of 5000r/min,
Re-ultrasonic dispersion 20min, is subsequently added into dibutyltin dilaurate, and dosage is phenylaminomethyl trimethoxy silane dosage
2wt%.Mixed liquor is warming up to 70 DEG C, 140min is to get modified manometer silicon dioxide for reaction, spare；
Step 3: 1200 parts of water, 100 parts of polyvinyl alcohol being added into reaction kettle, are warming up to 100 DEG C, stirring is until poly- second
Enol all dissolves, then is down to room temperature.Then 5 parts of lauryl sodium sulfate are added into mixed solution, 3.0 parts of steps (2) obtain
Modified manometer silicon dioxide, 4 parts of toluene di-isocyanate(TDI)s and the dibutyltin dilaurate arrived, wherein dibutyltindilaurylmercaptide
The dosage of cinnamic acid ester is the 2wt% of toluene di-isocyanate(TDI) dosage.It is stirred to react 50min, is discharged to get modified polyvinylalcohol glue
Stick.
Water resistance and adhesive strength test result show the time of coming unglued of glued board greater than 36h, and bonding strength reaches
3.3MPa。
Claims (10)
1. a kind of Nano-meter SiO_22The preparation method of Modified Polyvinyl Alcohol Based Waterborne Water adhesive, which comprises the following steps: (a)
The hydrolyzate that amino silicane coupling agent is prepared using organic solvent, amino silicane coupling agent and water, is then added into hydrolyzate
Nano silica and catalyst are simultaneously uniformly dispersed, and heating is reacted to obtain modified manometer silicon dioxide；(b) by polyvinyl alcohol
It is soluble in water, emulsifier, catalyst, modified manometer silicon dioxide, isocyanates are added, up to modified poly- second after being stirred to react
Enol adhesive.
2. a kind of Nano-meter SiO_2 according to claim 12The preparation method of Modified Polyvinyl Alcohol Based Waterborne Water adhesive, feature exist
In: the dosage of each substance is calculated as in step (a) with mass fraction: 6-8 parts of organic solvent, 1.4-2 parts of amino silicane coupling agent, water
1.4-2 parts, 10-15 parts of nano silica, wherein the dosage of catalyst is the 1-3wt% of amino silicane coupling agent dosage.
3. a kind of Nano-meter SiO_2 according to claim 12The preparation method of Modified Polyvinyl Alcohol Based Waterborne Water adhesive, feature exist
In: the dosage of each substance is calculated as in step (b) with mass fraction: 100 parts of polyvinyl alcohol, 1100-1400 parts of water, emulsifier 3-5
Part, 2.5-3 parts of modified manometer silicon dioxide, 3-6 parts of isocyanates, wherein the dosage of catalyst is the 1- of isocyanates dosage
3wt%.
4. a kind of Nano-meter SiO_2 according to claim 1-32The preparation method of Modified Polyvinyl Alcohol Based Waterborne Water adhesive,
It is characterized by: the organic solvent is one of ethyl acetate, acetone, toluene, dimethylbenzene.
5. a kind of Nano-meter SiO_2 according to claim 1-32The preparation method of Modified Polyvinyl Alcohol Based Waterborne Water adhesive,
It is characterized by: the amino silicane coupling agent be gamma-aminopropyl-triethoxy-silane, phenylaminomethyl trimethoxy silane,
One of N- β (aminoethyl)-γ-aminopropyltriethoxy diethoxy silane.
6. a kind of Nano-meter SiO_2 according to claim 1-32The preparation method of Modified Polyvinyl Alcohol Based Waterborne Water adhesive,
It is characterized by: the emulsifier is one of OP-10, lauryl sodium sulfate, nekal.
7. a kind of Nano-meter SiO_2 according to claim 1-32The preparation method of Modified Polyvinyl Alcohol Based Waterborne Water adhesive,
It is characterized by: the isocyanates be toluene di-isocyanate(TDI), hexamethylene diisocyanate, triphenyl methane -4,4 ', 4 "-three is different
One of cyanate.
8. a kind of Nano-meter SiO_2 according to claim 1-32The preparation method of Modified Polyvinyl Alcohol Based Waterborne Water adhesive,
It is characterized by: step (a) and step (b) catalyst are dibutyltin dilaurate.
9. a kind of Nano-meter SiO_2 according to claim 12The preparation method of Modified Polyvinyl Alcohol Based Waterborne Water adhesive, feature exist
In: 20-45min need to be stirred at normal temperature when preparing the hydrolyzate of amino silicane coupling agent in step (a), be added into hydrolyzate
20-40min is stirred with the rate of 4500-6000r/min after nano silica, re-ultrasonic dispersion 10-20min is subsequently added into
Mixed liquor is simultaneously warming up to 70-90 DEG C of reaction 100-140min by catalyst.
10. a kind of Nano-meter SiO_2 according to claim 12The preparation method of Modified Polyvinyl Alcohol Based Waterborne Water adhesive, feature
It is: when in step (b) with water-soluble Polyvinyl alcohol, polyvinyl alcohol-aqueous mixtures is first heated to 60-100 DEG C and are stirred straight
To being completely dissolved, it is then cooled to room temperature, adds stirring at normal temperature 30-50min after all materials.
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| CN110499098A (en) * | 2019-09-09 | 2019-11-26 | 佛山市大幸新材料有限公司 | A kind of antifouling protective agent of dumb light sheen ceramic tile |
| CN114605859A (en) * | 2022-03-11 | 2022-06-10 | 杭州金州高分子科技有限公司 | Water-resistant and high-temperature-resistant material and preparation method thereof |
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