CN104694050B - Glue with dry solidification at a slow speed and preparation method thereof pasted by a kind of invoice - Google Patents
Glue with dry solidification at a slow speed and preparation method thereof pasted by a kind of invoice Download PDFInfo
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- CN104694050B CN104694050B CN201510069079.8A CN201510069079A CN104694050B CN 104694050 B CN104694050 B CN 104694050B CN 201510069079 A CN201510069079 A CN 201510069079A CN 104694050 B CN104694050 B CN 104694050B
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Abstract
The invention discloses a kind of invoice and paste the glue with dry solidification at a slow speed, it contains silicon dioxide/polyvinyl alcohol hybrid material or metal-oxide/polyvinyl alcohol hybrid material, possibly together with high-ratio surface powder-deposit, prepare via following steps: the mixed solvent of methanol, second alcohol and water is thrown in reactor, is warming up to 65～85 DEG C；Add presoma, drip a certain amount of dilute hydrochloric acid or dilute alkaline soln, control the pH of system between 1～6；Being slowly added into polyvinyl acetate solid, stirring is until being completely dissolved, and continues insulation reaction 1～3h；Adding high-ratio surface powder-deposit, stirring reaction completely, cools down and stands to room temperature, obtain the glue of dry solidification at a slow speed.The glue of the present invention is after coating uses, and adhesion is strong and dry solidification speed is slow.
Description
Technical field
The present invention relates to a kind of glue, particularly relate to a kind of invoice and paste glue using dry solidification at a slow speed and preparation method thereof.
Background technology
In routine work and life, it is often necessary to use glue and paste various article, such as file, invoice, books etc..Most of glue, such as 502 glue, are all the glue of quick-dry type, and one is coated, several seconds or tens of second just can dry solidification, thus will need paste two objects tightly stick together.And once run into the situation needing to tear or re-paste, then be easy to damage the object (such as page, invoice etc.) that paste owing to glue has been fully cured to be dried, at this time we be accomplished by a kind of dry solidification speed compare slowly glue to meet this demand.
In prior art, the research about glue or adhesive is the most ripe, the most quick-drying, wink dry type glue, and slow curing type glue is the product needing large area to bond for plastic, building board etc. mostly.According to the retrieval of applicant, find the glue of the dry solidification at a slow speed the most not yet having suitable routine work and life to use.
Summary of the invention
The invention provides a kind of invoice and paste the glue with dry solidification at a slow speed, this kind of glue is after coating uses, and adhesion is strong and dry solidification speed is slow.
For achieving the above object, the present invention adopts the following technical scheme that
The glue with dry solidification at a slow speed pasted by a kind of invoice, and it contains silicon dioxide/polyvinyl alcohol hybrid material or metal-oxide/polyvinyl alcohol hybrid material.
Preferably, one or more combination in any during described metal-oxide is the oxide of titanium, zirconium, stannum, aluminum.
Preferably, described glue is not less than 500 m possibly together with high-ratio surface powder-deposit, the specific surface area of this high-ratio surface powder-deposit2/g。
Preferably, described high-ratio surface powder-deposit is one or more combination in any in Magnesiumaluminumsilicate, magnesium aluminometasilicate, aluminium hydroxide, fume colloidal silica, brucite.
A kind of method preparing the described invoice stickup use glue of dry solidification at a slow speed, comprises the following steps:
(1) mixed solvent of methanol, second alcohol and water is thrown in reactor, be warming up to 65～85 DEG C；
(2) add presoma, drip a certain amount of dilute hydrochloric acid or dilute alkaline soln, control the pH of system between 1～6；
(3) being slowly added into polyvinyl acetate solid, stirring is until being completely dissolved, and continues insulation reaction 1～3h；
(4) adding high-ratio surface powder-deposit, stirring reaction completely, cools down and stands to room temperature, obtains invoice of the present invention and pastes the glue with dry solidification at a slow speed.
Preferably, in described methanol, the mixed solvent of second alcohol and water, the mass ratio of first alcohol and water is 1:20～50, and the mass ratio of second alcohol and water is 1:1～30；The gross mass of mixed solvent and the mass ratio of polyvinyl acetate solid are 2～9:1.
Preferably, described dilute alkaline soln can be dilute NaOH solution, weak ammonia or dilute KOH solution, it is also possible to is that other have other dilute alkaline solns of similarity.
Preferably, one or more combination in any during described presoma is tetraethyl orthosilicate, MTES, butyl titanate, zirconium oxychloride, butter of tin, aluminum chloride, titanium tetrachloride.
Preferably, one or more combination in any during described powder body is Magnesiumaluminumsilicate, magnesium aluminometasilicate, aluminium hydroxide, fume colloidal silica, brucite.
Preferably, the mass ratio of described presoma and polyvinyl acetate solid is 1:10～30.
Preferably, the mass ratio of described powder body and polyvinyl acetate solid is 1:50～100.
Preferably, the mixing speed of step (4) is 500～1500 rpm.
According to technical scheme, presoma and polyvinyl acetate generation cohydrolysis, the former hydrolyzes and generates the Si oxide chain containing a lot-OH or metal-oxide chain, and the latter generates the polyvinyl alcohol containing some-OH；Both hydrolysis during can by-OH between dehydration condensation and link together, i.e. Organic substance polyvinyl alcohol and Si oxide or inorganic, metal oxide links together, and generates silicon dioxide/polyvinyl alcohol hybrid material or metal-oxide/polyvinyl alcohol hybrid material.For example, that utilize that tetraethyl orthosilicate correspondence generates is SiO2/ polyvinyl alcohol hybrid material, that utilize that butyl titanate correspondence generates is TiO2/ polyvinyl alcohol hybrid material, that utilize that butter of tin correspondence generates is SnO2/ polyvinyl alcohol hybrid material, other presomas are similar.
Due to containing silicon dioxide/polyvinyl alcohol hybrid material or metal-oxide/polyvinyl alcohol hybrid material, polyvinyl alcohol in the glue so prepared slowly comes off from Si oxide or metal-oxide and plays bonding effect, simultaneously because silicon dioxide/polyvinyl alcohol hybrid material or metal-oxide/polyvinyl alcohol hybrid material have stronger hydrophilic, the internal attraction of hybrid material combines a certain amount of hydrone, the volatilization of this kind of internal water molecule is very slow, and both reasons make the glue for preparing can dry solidification slowly.
Additionally, the present invention also with the addition of the powder body of high-specific surface area in glue, its effect is to utilize the specific surface area that it is huge, the polyvinyl alcohol freely slowly come off and internal water molecule are attracted to its pore structure, delay polyvinyl alcohol further and play the time of adhesive action, and make it possibly together with moisture after a very long time, solidification will not be completely dried, some occasion is facilitated to use, such as paste a/d, if finding in a few days, mistake easily can tear it down invoice re-posted, without causing completely because of dry solidification damaging invoice as common glue during tearing.
And, can't there is situation about being pasted not strongly because of its dry solidification overlong time in the product of the present invention, this is because in the hybrid structure of silicon dioxide/polyvinyl alcohol hybrid material or metal-oxide/polyvinyl alcohol hybrid material, Si oxide chain or metal-oxide chain contain a lot-OH, on the one hand it attracted polyvinyl alcohol molecule and internal water molecule, on the other hand provide the initial bonding strength suited the requirements, thus ensure just to have started the article such as the invoice pasted and can compare and be securely bonded together.
Detailed description of the invention
In order to be better understood from present invention, being described in further detail the present invention below in conjunction with specific embodiment, the concrete protection domain of the present invention is not limited by following embodiment.
Embodiment 1
The mixed solvent (wherein the mass ratio of first alcohol and water is 1:50, and the mass ratio of second alcohol and water is 1:1, and the gross mass of mixed solvent and the mass ratio of polyvinyl acetate solid are 2:1) of methanol, second alcohol and water is thrown in reactor, is warming up to 85 DEG C；Add 1 part of (weight portion) tetraethyl orthosilicate, drip a certain amount of dilute hydrochloric acid, control the pH of system between 1～6；Being slowly added into 10 parts of (weight portion) polyvinyl acetate solids, stirring is until being completely dissolved, and continues insulation reaction 1h；Adding 0.2(weight portion) (specific surface area is 837 m to part magnesium aluminometasilicate2/ g), stir 1.5h with 1500rpm rotating speed, cool down and stand to room temperature, obtain invoice and paste the glue with dry solidification at a slow speed, it contains silicon dioxide/polyvinyl alcohol hybrid material.
Embodiment 2
The mixed solvent (wherein the mass ratio of first alcohol and water is 1:20, and the mass ratio of second alcohol and water is 1:30, and the gross mass of mixed solvent and the mass ratio of polyvinyl acetate solid are 7:1) of methanol, second alcohol and water is thrown in reactor, is warming up to 70 DEG C；Add 3 parts of (weight portion) zirconium oxychlorides, drip a certain amount of dilute KOH solution, control the pH of system between 1～6；Being slowly added into 30 parts of (weight portion) polyvinyl acetate solids, stirring is until being completely dissolved, and continues insulation reaction 3h；Add the mixture (each material mixes) of 0.4 part of (weight portion) magnesium aluminometasilicate, aluminium hydroxide, fume colloidal silica and brucite with any weight ratio, 0.5h is stirred with 1000rpm rotating speed, cool down and stand to room temperature, obtaining invoice and paste the glue with dry solidification at a slow speed, it contains zirconium dioxide/polyvinyl alcohol hybrid material.
Embodiment 3
The mixed solvent (wherein the mass ratio of first alcohol and water is 1:30, and the mass ratio of second alcohol and water is 1:20, and the gross mass of mixed solvent and the mass ratio of polyvinyl acetate solid are 9:1) of methanol, second alcohol and water is thrown in reactor, is warming up to 65 DEG C；Add the mixture (two kinds of materials mix with any weight ratio) of 0.5 part of (weight portion) MTES and butyl titanate, drip a certain amount of weak ammonia, control the pH of system between 1～6；Being slowly added into 10 parts of (weight portion) polyvinyl acetate solids, stirring is until being completely dissolved, and continues insulation reaction 2h；Adding 0.1 part of (weight portion) fume colloidal silica, stir 1h with 500rpm rotating speed, cool down and stand to room temperature, obtain invoice and paste the glue with dry solidification at a slow speed, it contains silica-titania/polyvinyl alcohol hybrid material.
Embodiment 4
The mixed solvent (wherein the mass ratio of first alcohol and water is 1:40, and the mass ratio of second alcohol and water is 1:10, and the gross mass of mixed solvent and the mass ratio of polyvinyl acetate solid are 4:1) of methanol, second alcohol and water is thrown in reactor, is warming up to 85 DEG C；Add the mixture (each material mixes with any weight ratio) of 1 part of (weight portion) tetraethyl orthosilicate, butter of tin and aluminum chloride, drip a certain amount of dilute NaOH solution, control the pH of system between 1～6；Being slowly added into 30 parts of (weight portion) polyvinyl acetate solids, stirring is until being completely dissolved, and continues insulation reaction 3h；Add the mixture (two kinds of materials mix) of 0.5 part of (weight portion) Magnesiumaluminumsilicate and aluminium hydroxide with any weight ratio, 1.5h is stirred with 1500rpm rotating speed, cool down and stand to room temperature, obtaining invoice and paste the glue with dry solidification at a slow speed, it contains silicon dioxide-tin ash-alchlor/polyvinyl alcohol hybrid material.
Performance test:
A. the initial bonding strength of testing glue
The glue sample that Example 1 prepares, by bonding for two hardboard glue, then measures with tensile testing machine, and recording its adhesive force is 0.001N/mm2, meet the adhesive tension of conventional glue.
B. the testing glue dry solidification time
The glue sample that Example 1 prepares, under indoor temperature and damp condition, fasten with glue two invoices, after placing 7-14 days, still can intactly fully be torn it down by invoice.
Find out according to above-described embodiment and the performance test results, the glue of the present invention is after coating uses, adhesion is strong, be enough to the article secure adhesion by needing stickup together, ensure the needs of daily stickup, and this kind of dry solidification speed is slow, convenient in the case of occurring pasting mistake, intact paste is torn.
Claims (9)
1. the glue with dry solidification at a slow speed pasted by an invoice, it is characterised in that: the glue of this dry solidification at a slow speed contains dioxy
SiClx/polyvinyl alcohol hybrid material or metal-oxide/polyvinyl alcohol hybrid material；Described glue possibly together with high-ratio surface powder-deposit,
The specific surface area of this high-ratio surface powder-deposit is not less than 500m2/g。
Glue the most according to claim 1, it is characterised in that: described metal-oxide is the oxidation of titanium, zirconium, stannum, aluminum
One or more combination in any in thing.
Glue the most according to claim 1, it is characterised in that: described high-ratio surface powder-deposit is Magnesiumaluminumsilicate, metasilicic acid
One or more combination in any in magnalium, aluminium hydroxide, fume colloidal silica, brucite.
4. the method preparing glue described in aforementioned any claim, comprises the following steps:
(1) mixed solvent of methanol, second alcohol and water is thrown in reactor, be warming up to 65～85 DEG C；
(2) add presoma, drip a certain amount of dilute hydrochloric acid or dilute alkaline soln, control the pH of system between 1～6；
(3) being slowly added into polyvinyl acetate solid, stirring is until being completely dissolved, and continues insulation reaction 1～3h；
(4) adding high-ratio surface powder-deposit, stirring reaction completely, cools down and stands to room temperature, obtains invoice and pastes with doing at a slow speed
The glue of dry solidification.
Method the most according to claim 4, it is characterised in that: described methanol, second alcohol and water mixed solvent in methanol and
The mass ratio of water is 1:20～50, and the mass ratio of second alcohol and water is 1:1～30.
Method the most according to claim 4, it is characterised in that: the gross mass of described mixed solvent and polyvinyl acetate
The mass ratio of solid is 2～9:1.
Method the most according to claim 4, it is characterised in that: described presoma is tetraethyl orthosilicate, methyl triethoxy
One or more combination in any in silane, butyl titanate, zirconium oxychloride, butter of tin, aluminum chloride, titanium tetrachloride.
Method the most according to claim 4, it is characterised in that: described high-ratio surface powder-deposit is Magnesiumaluminumsilicate, metasilicic acid
One or more combination in any in magnalium, aluminium hydroxide, fume colloidal silica, brucite.
Method the most according to claim 4, it is characterised in that: described presoma and the mass ratio of polyvinyl acetate solid
For 1:10～30, and/or the mass ratio of described high-ratio surface powder-deposit and polyvinyl acetate solid is 1:50～100.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510069079.8A CN104694050B (en) | 2015-02-10 | 2015-02-10 | Glue with dry solidification at a slow speed and preparation method thereof pasted by a kind of invoice |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510069079.8A CN104694050B (en) | 2015-02-10 | 2015-02-10 | Glue with dry solidification at a slow speed and preparation method thereof pasted by a kind of invoice |
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| Publication Number | Publication Date |
|---|---|
| CN104694050A CN104694050A (en) | 2015-06-10 |
| CN104694050B true CN104694050B (en) | 2016-08-24 |
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| CN201510069079.8A Expired - Fee Related CN104694050B (en) | 2015-02-10 | 2015-02-10 | Glue with dry solidification at a slow speed and preparation method thereof pasted by a kind of invoice |
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| CN110093105A (en) * | 2019-04-11 | 2019-08-06 | 上海洛法化工有限公司 | A kind of novel low-odor latex and its preparation process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314446A (en) * | 2000-03-17 | 2001-09-26 | 雅马哈株式会社 | Adhesion agent |
| CN102220055A (en) * | 2011-04-28 | 2011-10-19 | 陈凯 | Coating paint for ink-jetting CTP (cytidine triphosphate) plate, printing plate base and preparation method thereof |
| CN103820945A (en) * | 2014-03-12 | 2014-05-28 | 东华大学 | Preparation method of organic/inorganic hybridization nano super-hydrophobic fiber film |
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2015
- 2015-02-10 CN CN201510069079.8A patent/CN104694050B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314446A (en) * | 2000-03-17 | 2001-09-26 | 雅马哈株式会社 | Adhesion agent |
| CN102220055A (en) * | 2011-04-28 | 2011-10-19 | 陈凯 | Coating paint for ink-jetting CTP (cytidine triphosphate) plate, printing plate base and preparation method thereof |
| CN103820945A (en) * | 2014-03-12 | 2014-05-28 | 东华大学 | Preparation method of organic/inorganic hybridization nano super-hydrophobic fiber film |
Non-Patent Citations (2)
| Title |
|---|
| 溶胶凝胶法聚醋酸乙烯酯/二氧化硅有机无机杂化材料的制备及表征;袁坚等;《武汉理工大学学报》;20010228;第23卷(第2期);第1-3页 * |
| 聚乙烯醇/二氧化硅共混膜的制备及耐温、耐溶剂性能研究;邓国宏等;《高分子材料科学与工程》;20011130;第17卷(第6期);第122-125页 * |
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Granted publication date: 20160824 Termination date: 20210210 |