CN114574142A - Moisture-proof high-strength sliding plate binder - Google Patents
Moisture-proof high-strength sliding plate binder Download PDFInfo
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- CN114574142A CN114574142A CN202210050202.1A CN202210050202A CN114574142A CN 114574142 A CN114574142 A CN 114574142A CN 202210050202 A CN202210050202 A CN 202210050202A CN 114574142 A CN114574142 A CN 114574142A
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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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
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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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the field of binders, and discloses a moisture-proof high-strength binder for a sliding plate, which comprises a material A and a material B, wherein the weight ratio of the material A to the material B is (0.8-1.2): 1; the material A comprises the following components in parts by weight: 40-70 parts of polyhydric alcohol, 20-50 parts of polyvinyl alcohol, 1-5 parts of stabilizer, 1-2 parts of penetrating agent and 0.1-1 part of catalyst; the material B comprises the following components in parts by weight: 30-60 parts of aminosilane modified polyisocyanate compound and 10-15 parts of coupling agent. The polyisocyanate compound is modified by grafting aminosilane, and the hydrolysis resistance and the bonding strength of the bonding agent are improved by modification; polyvinyl alcohol with a certain alcoholysis degree and molecular weight is used in the formula of the adhesive, so that the tensile property of the adhesive is improved.
Description
Technical Field
The invention relates to the field of adhesives, in particular to a moisture-proof high-strength adhesive for a sliding plate.
Background
The skateboard is a road surface sliding tool and is also an apparatus for extreme sports. In the process of skateboard sports, athletes perform technical exhibition in a specific field by applying various skills, have good joyfulness, interest, irritation and appreciation, are gradually accepted and welcomed by the public, and the demand of domestic skateboards is continuously increased.
Currently, the commercially available skateboard is mainly made of wood, and particularly hard maple represented by maple canada. The hard maple wood has the main advantages of hard texture, very high friction resistance and abrasion resistance, moderate elasticity, good steam bending performance, good processing performance in the process of processing and manufacturing the sliding plate, good elasticity of the surface of the prepared sliding plate and high strength. However, the problems of the hard maple during the use process are mainly two points: one is common diseases of wood, which has poor water resistance and weather resistance, and is easy to cause poor elasticity due to water absorption in a humid environment and break in the using process; secondly, the hard maple is heavy and cannot meet the requirement of pursuing light weight of athletes.
As for the second point, some patents have disclosed some skateboards using new materials, for example, chinese patent publication No. CN104097374A discloses a skateboard panel using new materials, which is composed of prepreg tape layers and polyurethane layers. The prepreg tape layer is formed by 100 parts of glass fiber reinforced thermoplastic resin composite material unidirectional prepreg tape laying, and the polyurethane layer is 5-10 parts of sheet-shaped thermoplastic polyurethane. The obtained sliding plate has improved water resistance, and is not easy to warp and peel after contacting water. The preparation method can completely avoid using glue, reduce the gluing process and reduce the pollution in the processing process; in addition, the sliding plate made of the glass fiber reinforced thermoplastic composite material has thinner plate surface and higher strength.
However, in the preparation process of the traditional mainstream wooden sliding plate, no effective moisture-proof and weather-proof binder is available, so that a large number of wooden sliding plates are easy to damage due to moisture permeation in the use process, economic loss is brought to athletes, and the safety of the sliding plates is also influenced.
Disclosure of Invention
The invention aims to solve the problems that a hard maple slide plate in the prior art is easy to absorb moisture and absorb water, and the strength and elasticity are reduced, and provides a moisture-proof high-strength slide plate binder.
In order to achieve the purpose, the invention adopts the following technical scheme:
a moisture-proof high-strength sliding plate binder comprises a material A and a material B in a weight ratio of (0.8-1.2) to 1; the material A comprises the following components in parts by weight: 40-70 parts of polyhydric alcohol, 20-50 parts of polyvinyl alcohol, 1-5 parts of stabilizer, 1-2 parts of penetrating agent and 0.1-1 part of catalyst; the material B comprises the following components in parts by weight: 30-60 parts of aminosilane modified polyisocyanate compound and 10-15 parts of coupling agent.
In the use process of the skateboard, athletes need to carry out various fancy motions and have certain requirements on the tensile strength of the skateboard adhesive, so on the basis of the traditional polyurethane adhesive, a certain amount of polyvinyl alcohol is added into the components, and a plurality of hydrogen bonds are formed between a large amount of hydroxyl groups in the polyvinyl alcohol and ether bonds and amino acid methyl esters in the polyurethane for crosslinking, so that the tensile strength of the adhesive is improved. On the other hand, in order to solve the problem that the hydrolysis resistance of the adhesive is reduced due to the addition of polyvinyl alcohol, an aminosilane modified polyisocyanate compound is modified by aminosilane to form an organosilicon waterproof layer, so that the hydrolysis resistance and the moisture resistance of the adhesive are improved.
Preferably, the preparation method of the aminosilane-modified polyisocyanate compound is as follows: the preparation method of the aminosilane modified polyisocyanate compound comprises the following steps: mixing and stirring 4-8 parts by mass of aminosilane, 20-30 parts by mass of polyisocyanate compound and 20-40 parts by mass of solvent at 60-80 ℃ in a nitrogen atmosphere for reacting for 2-6 hours, and removing the solvent to obtain an intermediate product; at 45-65 ℃ and under the nitrogen atmosphere, 15-25 parts by mass of polyhydric alcohol and 70-90 parts by mass of intermediate product, and 80-100 parts by mass of intermediate product
And mixing and stirring the solvents for reaction for 1-3 h, and removing the solvents to obtain the aminosilane modified polyisocyanate compound.
And modifying the polyisocyanate compound by adopting aminosilane, so that a reaction group in the polyisocyanate compound reacts with an amino group in the aminosilane, and introducing an organic silicon structure into the tail end of the polyisocyanate compound. The organic silicon structure can play an effective waterproof effect, and the cross-linking formed by subsequent curing is reduced. Meanwhile, the amino groups in the remaining unreacted aminosilane can further increase the active functional groups in the polyisocyanate compound, thereby enhancing the crosslinking strength of the polyisocyanate compound. If the amount of the aminosilane is too small, a good protection effect cannot be achieved; if the amount of the aminosilane is too large, it may result in too many silicone structures being attached to the polyisocyanate compound, resulting in an increased difficulty in contacting the aminosilane-modified polyisocyanate compound with other reactants during crosslinking, resulting in an increased curing time. And (3) carrying out prepolymerization on the polyisocyanate subsequently, wherein the number of isocyanate groups is more than that of hydroxyl groups in the reaction process, and a prepolymer with an end group of-NCO can be obtained after the reaction. The polyisocyanate compound is pre-polymerized to a certain degree, so that the forming speed of the binder can be controlled to meet the requirement.
Preferably, the polyisocyanate compound is one of diphenylmethane diisocyanate, isophorone diisocyanate, or dicyclohexylmethane diisocyanate.
Preferably, the aminosilane is one of aminopropyltrimethoxysilane and aminopropyltriethoxysilane. After the reaction, the aminopropyl can form two carbon-carbon bonds between a nitrogen atom and a silicon atom, so that a reasonable distance is formed between the organosilicon structure and a reaction main chain, and the subsequent curing process is not influenced.
Preferably, the polyol is one or more of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, neopentyl glycol, polyester polyol and polyether polyol.
Preferably, the molecular weight of the polyvinyl alcohol is 15000-35000, and the alcoholysis degree is 86-89%. The molecular weight of the polyvinyl alcohol is related to the polymerization degree of the polyvinyl alcohol, and if the molecular weight of the polyvinyl alcohol is too high, the number of rigid carbon chains in a system is too large, and the strength of the binder is influenced. The alcoholysis degree of the polyvinyl alcohol determines the number of hydroxyl groups in the polyvinyl alcohol, when the number of the hydroxyl groups is too small, sufficient hydrogen bonds and crosslinking cannot be formed, and the function of enhancing the tensile strength of the binder cannot be achieved, and when the number of the hydroxyl groups is too large, the polyvinyl alcohol is crosslinked too much, so that a good mixed and crosslinked network cannot be formed with a system.
Preferably, the coupling agent is a silane coupling agent.
Preferably, the stabilizer is nano titanium dioxide or nano aluminum oxide.
Preferably, the penetrant is at least one of span and Tween.
Preferably, the catalyst is an organotin catalyst.
Therefore, the invention has the following beneficial effects: (1) the amino silane is adopted to modify the polyisocyanate compound, so that the hydrolysis resistance and the bonding strength of the bonding agent are improved; (2) and the polyvinyl alcohol with a certain alcoholysis degree is adopted to improve the tensile property of the adhesive.
Detailed Description
The invention is further described with reference to specific embodiments. It is to be understood that these examples are suitable for illustrating the basic features and advantages of the invention, and the invention is not to be limited in scope by the following examples; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions used in routine experiments.
Not specifically illustrated in the following examples, all starting materials are commercially available or prepared by methods conventional in the art.
Example 1
(1) Preparation of aminosilane-modified polyisocyanate compound: uniformly mixing 6 parts by weight of aminopropyltrimethoxysilane, 25 parts by weight of diphenylmethane diisocyanate and 30 parts by weight of toluene at 70 ℃ in a nitrogen atmosphere, stirring for reacting for 4 hours, and removing the solvent to obtain an intermediate product; uniformly mixing 20 parts by mass of polyester polyol, 80 parts by mass of intermediate product and 90 parts by mass of toluene at 55 ℃ in a nitrogen atmosphere, stirring for reacting for 2 hours, and removing the solvent to obtain an aminosilane-modified polyisocyanate compound;
(2) preparing a binder: the moisture-proof high-strength skateboard adhesive comprises a material A and a material B in a mass ratio of 1:1, wherein the material A comprises the following components in parts by weight: 60 parts of ethylene glycol and 1, 3-propylene glycol in a mass ratio of 1:2, 30 parts of polyvinyl alcohol (with the molecular weight of 25000 and the alcoholysis degree of 88%), 3 parts of nano titanium dioxide, 1 part of span and 0.5 part of dibutyltin dilaurate; the material B comprises the following components in parts by weight: 45 parts of aminosilane modified polyisocyanate compound and 12 parts of vinyl triethoxysilane;
(3) preparing a binder: adding the ethylene glycol, the 1, 3-propylene glycol, the polyvinyl alcohol, the nano titanium dioxide and the span in the material A into a reaction kettle according to a proportion, starting stirring, heating to 95 ℃, adding the dibutyltin dilaurate when the moisture content of the material is less than 0.06% through vacuum dehydration, and uniformly stirring to obtain the material A; and weighing the raw materials of the material B in proportion, and uniformly stirring to obtain the material B.
When in use, the material A and the material B are mixed and stirred uniformly according to the formula amount to obtain the moistureproof high-strength binder for the sliding plate.
Example 2
(1) Preparation of aminosilane-modified polyisocyanate compound: uniformly mixing 4 parts by mass of aminopropyltriethoxysilane, 20 parts by mass of isophorone diisocyanate and 20 parts by mass of toluene at 60 ℃ in a nitrogen atmosphere, stirring for reaction for 6 hours, and removing the solvent to obtain an intermediate product; uniformly mixing 15 parts by mass of polyether polyol, 70 parts by mass of intermediate product and 80 parts by mass of toluene at 65 ℃ in a nitrogen atmosphere, stirring for reacting for 1h, and removing the solvent to obtain an aminosilane-modified polyisocyanate compound;
(2) preparing a binder: the moisture-proof high-strength skateboard adhesive comprises a material A and a material B in a mass ratio of 0.8:1, wherein the material A comprises the following components in parts by weight: 40 parts of neopentyl glycol, 20 parts of polyvinyl alcohol (the molecular weight is 15000, and the alcoholysis degree is 89%), 1 part of nano titanium dioxide, 1 part of tween and 0.1 part of dibutyltin dilaurate; the material B comprises the following components in parts by weight: 30 parts of amino silane modified polyisocyanate compound and 10 parts of isobutyl triethoxysilane;
(3) preparing a binder: adding neopentyl glycol, polyvinyl alcohol, nano titanium dioxide and tween in the material A into a reaction kettle in proportion, starting stirring, heating to 90 ℃, adding dibutyltin dilaurate when the moisture content of the material is less than 0.06% through vacuum dehydration, and uniformly stirring to obtain the material A; and weighing the raw materials of the material B in proportion, and uniformly stirring to obtain the material B.
When in use, the material A and the material B are mixed and stirred uniformly according to the formula amount, and the moisture-proof high-strength binder for the sliding plate is obtained.
Example 3
(1) Preparation of aminosilane-modified polyisocyanate compound: uniformly mixing 8 parts by mass of aminopropyltriethoxysilane, 30 parts by mass of dicyclohexylmethane diisocyanate and 40 parts by mass of xylene at 80 ℃ in a nitrogen atmosphere, stirring for reacting for 2 hours, and removing the solvent to obtain an intermediate product; uniformly mixing 25 parts by mass of 1, 4-butanediol, 90 parts by mass of intermediate product and 100 parts by mass of xylene at 45 ℃ in a nitrogen atmosphere, stirring for reacting for 3 hours, and removing the solvent to obtain an aminosilane-modified polyisocyanate compound;
(2) preparing a binder: the moisture-proof high-strength skateboard adhesive comprises a material A and a material B in a mass ratio of 1.2:1, wherein the material A comprises the following components in parts by weight: 70 parts of 1, 3-propylene glycol and 1, 4-butanediol with the mass ratio of 1:1, 50 parts of polyvinyl alcohol (with the molecular weight of 35000 and the alcoholysis degree of 86%), 5 parts of nano aluminum oxide, 1 part of span and 1 part of stannous octoate; the material B comprises the following components in parts by weight: 60 parts of aminosilane modified polyisocyanate compound and 15 parts of vinyl trimethoxy silane;
(3) preparing a binder: adding 1, 3-propylene glycol, 1, 4-butanediol, polyvinyl alcohol, nano-alumina and span in the material A into a reaction kettle according to a proportion, starting stirring, heating to 95 ℃, adding stannous octoate when the moisture content of the material is less than 0.06% through vacuum dehydration, and uniformly stirring to obtain the material A; and weighing the raw materials of the material B in proportion, and uniformly stirring to obtain the material B.
When in use, the material A and the material B are mixed and stirred uniformly according to the formula amount, and the moisture-proof high-strength binder for the sliding plate is obtained.
Example 4
(1) Preparation of aminosilane-modified polyisocyanate compound: uniformly mixing 5 parts by mass of aminopropyltriethoxysilane, 23 parts by mass of dicyclohexylmethane diisocyanate and 35 parts by mass of cyclohexane at 65 ℃ in a nitrogen atmosphere, stirring for reaction for 4.5 hours, removing a solvent to obtain an intermediate product, uniformly mixing 25 parts by mass of polyether polyol, 85 parts by mass of the intermediate product and 95 parts by mass of cyclohexane at 45 ℃ in the nitrogen atmosphere, stirring for reaction for 3 hours, and removing the solvent to obtain an aminosilane modified polyisocyanate compound; (2) preparing a binder: the moisture-proof high-strength skateboard adhesive comprises a material A and a material B in a mass ratio of 1.1:1, wherein the material A comprises the following components in parts by weight: 55 parts of 1, 4-butanediol, 25 parts of polyvinyl alcohol (the molecular weight is 30000 and the alcoholysis degree is 88%), 4 parts of nano-alumina, 1 part of span and tween with the mass ratio of 1:1 and 0.6 part of stannous octoate; the material B comprises the following components in parts by weight: 50 parts of aminosilane modified polyisocyanate compound and 13 parts of vinyl triethoxysilane;
(3) preparing a binder: adding 1, 4-butanediol, polyvinyl alcohol, nano-alumina, span and tween in the material A into a reaction kettle according to a proportion, starting stirring, heating to 100 ℃, adding stannous octoate when the moisture content of the material is less than 0.06% through vacuum dehydration, and uniformly stirring to obtain a material A; and weighing the raw materials of the material B in proportion, and uniformly stirring to obtain the material B.
When in use, the material A and the material B are mixed and stirred uniformly according to the formula amount, and the moisture-proof high-strength binder for the sliding plate is obtained.
Example 5
(1) Preparation of aminosilane-modified polyisocyanate compound: uniformly mixing 5 parts by mass of aminopropyltrimethoxysilane, 25 parts by mass of isophorone diisocyanate and 30 parts by mass of toluene at 75 ℃ in a nitrogen atmosphere, stirring for reaction for 3.5 hours, and removing the solvent to obtain an intermediate product; uniformly mixing 20 parts by mass of ethylene glycol, 90 parts by mass of an intermediate product and 85 parts by mass of toluene at 50 ℃ in a nitrogen atmosphere, stirring for reacting for 2.5 hours, and removing the solvent to obtain an aminosilane-modified polyisocyanate compound;
(2) preparing a binder: the moisture-proof high-strength skateboard adhesive comprises a material A and a material B in a mass ratio of 0.9:1, wherein the material A comprises the following components in parts by weight: 65 parts of polyester polyol, 35 parts of polyvinyl alcohol (with the molecular weight of 20000 and the alcoholysis degree of 88%), 5 parts of nano titanium dioxide, 2 parts of span and 1 part of dibutyltin dilaurate; the material B comprises the following components in parts by weight: 40 parts of amino silane modified polyisocyanate compound and 15 parts of vinyl trimethoxy silane;
(3) preparing a binder: adding the polyester polyol, the polyvinyl alcohol, the nano titanium dioxide and the span in the material A into a reaction kettle in proportion, starting stirring, heating to 95 ℃, performing vacuum dehydration until the moisture content of the material is less than 0.06%, adding the dibutyltin dilaurate, and uniformly stirring to obtain the material A; and weighing the raw materials of the material B in proportion, and uniformly stirring to obtain the material B.
When in use, the material A and the material B are mixed and stirred uniformly according to the formula amount to obtain the moistureproof high-strength binder for the sliding plate.
Comparative example 1
This comparative example is a commercially available polyurethane wood binder.
Comparative example 2
This comparative example differs from example 1 only in that the modification of step (1) was not carried out and diphenylmethane diisocyanate was used in place of the modified diphenylmethane diisocyanate in feed B.
Comparative example 3
This comparative example differs from example 1 only in that 16 parts aminopropyltrimethoxysilane were added during the modification in step (1).
Comparative example 4
This comparative example differs from example 1 only in that the preparation process of step (1) is: uniformly mixing 6 parts by weight of aminopropyltrimethoxysilane, 25 parts by weight of diphenylmethane diisocyanate and 30 parts by weight of toluene at 70 ℃ in a nitrogen atmosphere, stirring for reaction for 4 hours, and removing the solvent to obtain the aminosilane-modified polyisocyanate compound.
Comparative example 5
This comparative example differs from example 1 only in that, instead of polyvinyl alcohol, an equal proportion of polyester polyol is added to the charge A.
Comparative example 6
This comparative example differs from example 1 only in that polyvinyl alcohol with a molecular weight of 100000 is used in batch a.
Comparative example 7
This comparative example differs from example 1 only in that a polyvinyl alcohol with an alcoholysis degree of 78% is used in charge A.
Comparative example 8
This comparative example differs from example 1 only in that a polyvinyl alcohol with a degree of alcoholysis of 98% is used in batch A.
The properties of the binders prepared in examples 1 to 5 and comparative examples 1 to 8 were measured. The tensile strength and the peel strength of the adhesive in the bonding of the wood board are measured according to the specification of GB/T7124-2008 'determination of tensile shear strength of the adhesive (rigid material to rigid material)'; and (4) measuring the water seepage speed of the wood boards obtained by bonding by using a water seepage instrument. During the measurement, the thickness of the adhesive layer was 0.2mm, and the water pressure of permeation was 50.5kPa, the results are shown in Table 1.
Table 1 binder performance test results
| Group of | Tensile Strength (MPa) | Peel strength (kN/m) | Water seepage speed (mL/s) |
| Example 1 | 24.5 | 3.32 | 8.10×10-5 |
| Example 2 | 23.2 | 3.25 | 1.05×10-4 |
| Example 3 | 24.1 | 3.29 | 8.77×10-5 |
| Example 4 | 25.7 | 3.63 | 9.93×10-5 |
| Example 5 | 21.0 | 3.38 | 7.42×10-5 |
| Comparative example 1 | 23.6 | 3.21 | 1.19×10-3 |
| Comparative example 2 | 19.5 | 2.99 | 2.77×10-3 |
| Comparative example 3 | 24.1 | 3.21 | 5.59×10-5 |
| Comparative example 4 | 17.3 | 2.77 | 1.77×10-4 |
| Comparative example 5 | 15.3 | 2.38 | 8.42×10-5 |
| Comparative example 6 | 16.9 | 2.26 | 9.95×10-5 |
| Comparative example 7 | 20.4 | 2.54 | 1.01×10-4 |
| Comparative example 8 | 22.5 | 3.09 | 3.56×10-4 |
As can be seen from table 1, in examples 1 to 5, aminosilane is used to modify a part of polyisocyanate in the preparation process of the binder, a certain amount of organosilicon is introduced into the binder, and the stability of the organosilicon provides a waterproof effect, thereby reducing the hydrolysis of chemical bonds; in addition, the dosage of the aminosilane is controlled to ensure that the adhesive has enough strength. Meanwhile, polyvinyl alcohol with specific molecular weight and alcoholysis degree is used in the preparation process, and the strength of the adhesive is improved by utilizing the fact that the long chain and a large number of hydroxyl groups of the polyvinyl alcohol directly generate more crosslinking and interaction with a polyisocyanate compound and aminosilane. Compared with comparative example 1, examples 1-5 have tensile strength and peel strength comparable to or better than commercial adhesives, while having better water resistance, and are more conducive to the use of adhesives in the preparation of skateboards. In the actual use process, the bonding strength of the bonding agents prepared in the embodiments 1-5 is not obviously changed after being wetted, while the bonding strength of the commercially available bonding agents is obviously reduced after being wetted, and the wood boards are easy to peel off.
Comparative example 2 the polyisocyanate compound was not modified during the preparation of the binder, so the water permeation rate was significantly higher than in examples 1-5 and the mechanical properties were lower than in examples 1-5 during the test, indicating that the aminosilane-modified binder can enhance the water and moisture resistance of the binder. Comparative example 3, too much aminosilane was added during the modification process, and although the strength and water permeation rate were both good, it was found in practical use that the curing time was very long (more than 30min) due to too much aminosilane, which limited the practical production efficiency, and thus it was difficult to meet the requirements. Comparative example 4, which does not prepolymerize the polyisocyanate compound, may result in a longer binder formation process, which is not advantageous for use, and the tensile strength under the same test conditions is much lower than in examples 1-5.
Comparative example 5, in which polyvinyl alcohol was not used, had tensile strength and peel strength lower than those of examples 1 to 5, indicating that the interaction between polyvinyl alcohol and polyisocyanate compound, aminosilane, etc. has an important effect on the adhesive strength of the adhesive. The polyvinyl alcohol used in comparative example 6 has an excessively large molecular weight, which results in failure to form a sufficient crosslinked network upon reaction with the polyisocyanate compound, and thus, the adhesive strength is impaired. In comparative example 7, a polyvinyl alcohol having too low alcoholysis was used, and it was possible that sufficient interaction could not be formed due to insufficient number of hydroxyl groups. Comparative example 8, which uses a polyvinyl alcohol with a higher alcoholysis degree, although it is more favorable for the formation of a crosslinked network in the binder, the excessive amount of hydroxyl groups causes a significant decrease in the water resistance of the binder.
Claims (10)
1. A moisture-proof high-strength sliding plate binder is characterized by comprising a material A and a material B in a weight ratio of (0.8-1.2) to 1; the material A comprises the following components in parts by weight: 40-70 parts of polyhydric alcohol, 20-50 parts of polyvinyl alcohol, 1-5 parts of stabilizer, 1-2 parts of penetrating agent and 0.1-1 part of catalyst; the material B comprises the following components in parts by weight: 30-60 parts of aminosilane modified polyisocyanate compound and 10-15 parts of coupling agent.
2. The moisture-proof high-strength skateboard adhesive as claimed in claim 1, wherein the aminosilane-modified polyisocyanate compound is prepared by: mixing and stirring 4-8 parts by mass of aminosilane, 20-30 parts by mass of polyisocyanate compound and 20-40 parts by mass of solvent at 60-80 ℃ in a nitrogen atmosphere for reacting for 2-6 hours, and removing the solvent to obtain an intermediate product; mixing and stirring 15-25 parts by mass of polyol, 70-90 parts by mass of intermediate product and 80-100 parts by mass of solvent at 45-65 ℃ in nitrogen atmosphere for reaction for 1-3 h, and removing the solvent to obtain the aminosilane modified polyisocyanate compound.
3. The moisture-proof high-strength skateboard adhesive according to claim 2, wherein the polyisocyanate compound is one of diphenylmethane diisocyanate, isophorone diisocyanate or dicyclohexylmethane diisocyanate.
4. The moisture-proof high-strength skateboard adhesive according to claim 2, wherein the aminosilane is one of aminopropyltrimethoxysilane and aminopropyltriethoxysilane.
5. The moisture-proof high-strength skateboard adhesive according to claim 2, wherein the polyol is one or more of ethylene glycol, 1, 3-propylene glycol, 1, 4-butylene glycol, neopentyl glycol, polyester polyol and polyether polyol.
6. The moisture-proof high-strength skateboard adhesive as claimed in claim 1, wherein the polyvinyl alcohol has a molecular weight of 15000-35000 and an alcoholysis degree of 86-89%.
7. The moisture-proof high-strength skateboard adhesive according to claim 1, wherein the coupling agent is a silane coupling agent.
8. The moisture-proof high-strength skateboard adhesive according to claim 1, wherein the stabilizer is nano titanium dioxide or nano aluminum oxide.
9. The moisture-proof high-strength skateboard adhesive according to claim 1, wherein the penetrant is at least one of span and temperature.
10. The moisture-proof high-strength skateboard adhesive according to claim 1, wherein the catalyst is an organotin catalyst.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116769374A (en) * | 2023-07-18 | 2023-09-19 | 湖北九阳防水材料科技有限公司 | Waterproof coating for metal roof |
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