CN109181618B - Formaldehyde-release-free environment-friendly adhesive for solid wood composite floor and preparation method thereof - Google Patents
Formaldehyde-release-free environment-friendly adhesive for solid wood composite floor and preparation method thereof Download PDFInfo
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- CN109181618B CN109181618B CN201811155071.3A CN201811155071A CN109181618B CN 109181618 B CN109181618 B CN 109181618B CN 201811155071 A CN201811155071 A CN 201811155071A CN 109181618 B CN109181618 B CN 109181618B
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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
- C09J175/08—Polyurethanes from polyethers
-
- 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
-
- 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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
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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
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
Abstract
The invention belongs to the technical field of preparation of high polymer materials, and particularly relates to a formaldehyde-release-free environment-friendly adhesive for solid wood composite floors and a preparation method thereof. The raw materials comprise the following components in percentage by mass: 65% -75% of polyether type dihydric alcohol; 18% -25% of diisocyanate; 3% -7% of a chain extender; 0.1 to 0.3 percent of antioxidant; 0.5 to 3 percent of superfine inorganic filler; 0.5 to 1.5 percent of coupling agent; 0.008 to 0.03 percent of catalyst. The solid content of the adhesive prepared by the invention is 100%, the adhesive can be coated among different structural layers of the composite floor through powder, and the adhesive can also be prepared into a film with a certain uniform thickness to be arranged among the structural layers of the floor, so that the uniformity of gluing is ensured, and the bonding strength is ensured; the prepared adhesive has high toughness and bonding strength, low cost and remarkable economic benefit, and achieves the aim of zero formaldehyde release in the use process of the floor.
Description
Technical Field
The invention belongs to the technical field of preparation of high polymer materials, and particularly relates to a formaldehyde-release-free environment-friendly adhesive for solid wood composite floors and a preparation method thereof.
Background
The solid wood composite floor is widely applied to hotels, markets and home decoration because of the advantages of attractive appearance, elegance, good structural stability and the like. Composite solid wood floors are first becoming popular in the european and american countries, and at present, composite floors are in the rapid development stage in China. In the preparation process of the composite floor, a large amount of adhesive is needed to be used and mainly coated among the multilayer structures of the composite floor so as to ensure the stability of the overall structure of the floor. At present, the widely used adhesives are mainly urea formaldehyde glue and imported powder glue (Nobel glue), wherein the used urea formaldehyde glue is basically self-made by floor manufacturers in China, and the defects are that formaldehyde is released unstably, environmental protection exceeds the standard easily, and in addition, the bonding strength is not high. The Nobel adhesive is imported from Europe and America, has high viscosity, is not easy to use in the production process, is easy to cause uneven gluing, and influences the bonding strength. In addition, although the formaldehyde emission of the nobel gum can reach the E1 standard, the formaldehyde emission is still the case. Along with the increasingly strict requirements of people on living environment, zero release of formaldehyde in the floor is a development trend in the future, so that the development of the formaldehyde-free environment-friendly adhesive has wide practical and application values.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a formaldehyde-release-free environment-friendly adhesive for solid wood composite floors. The prepared adhesive has high toughness and bonding strength, low cost and remarkable economic benefit, and achieves the aim of zero formaldehyde release in the use process of the floor; the invention also provides a preparation method of the composition.
The formaldehyde-free release environment-friendly adhesive for the solid wood composite floor comprises the following raw materials in parts by mass:
wherein:
the molecular weight of the polyether glycol is between 2500 and 3000.
The polyether type dihydric alcohol is one or a mixture of a plurality of polyoxyethylene dihydric alcohol, polyoxypropylene dihydric alcohol, polytetrahydrofuran dihydric alcohol or vinyl polymer grafted polyether dihydric alcohol in any proportion; polytetrahydrofuran diol is preferred.
The diisocyanate is one of 4,4' -diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, toluene isocyanate or phenylene-1, 4-diisocyanate; 4,4' -diphenylmethane diisocyanate (MDI-100) is preferred.
The chain extender is one or a mixture of more of ethylene glycol, 1, 4-butanediol, 1, 2-propanediol, 1, 3-propanediol or 2-methyl-1, 3-propanediol in any proportion; 1, 4-Butanediol (BDO) is preferred.
The antioxidant is one or more of hindered phenol antioxidant or phosphite antioxidant which are mixed in any proportion; preferably pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (1010), bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite (626), tris [2, 4-di-tert-butylphenyl ] phosphite (168) or didecyl-glycol thiodipropionate (DLTDP), and more preferably pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (1010).
The superfine inorganic filler is one or more of calcium carbonate, magnesium carbonate, talcum powder, titanium pigment, white carbon black or kaolin which are mixed in any proportion, and the mesh number of the superfine inorganic filler is more than or equal to 1000 meshes.
The coupling agent is one or a mixture of more of polyolefins, polyolefin salts, alkenyl organosilanes, titanate or chromium complexes in any proportion; vinyl triethoxysilane (A151) is preferred.
The catalyst is one of organic bismuth catalysts or titanate catalysts, and is preferably an organic bismuth catalyst DY-20 (the manufacturer is Bridgnesia).
The preparation method of the formaldehyde-free release environment-friendly adhesive for the solid wood composite floor comprises the steps of mixing and heating polyether type dihydric alcohol, an antioxidant, a catalyst and a coupling agent to 130-150 ℃, and fully and uniformly mixing; heating diisocyanate to 45-55 ℃, and heating the chain extender to 45-55 ℃; the heated raw materials are metered and then injected into an extruder through a high-speed stirring head, the metered superfine inorganic filler is added into the rear section of the extruder, the mixed materials are fully reacted and plasticized in a screw rod, and the formaldehyde-free release environment-friendly adhesive is obtained after granulation by an underwater cutting system.
The application of the formaldehyde-free release environment-friendly adhesive for the solid wood composite floor is to prepare the formaldehyde-free release environment-friendly adhesive into a hot melt adhesive sheet, place the adhesive sheet between floor layers, and finally obtain the solid wood composite floor through hot pressing.
Compared with the prior art, the invention has the following beneficial effects:
(1) the adhesive disclosed by the invention has no formaldehyde release in the preparation and use processes, and is environment-friendly and non-toxic in the life cycle of the whole product; compared with imported Nobel glue, the adhesive disclosed by the invention is low in cost, and has the advantages of cost and outstanding economic benefits.
(2) The solid content of the adhesive is 100%, the adhesive can be coated among different structural layers of the composite floor through powder, and the adhesive can also be prepared into a film with a certain uniform thickness to be arranged among the structural layers of the floor, so that the uniformity of gluing is ensured, and the bonding strength is ensured.
(3) The superfine inorganic filler is added into the adhesive, so that the toughness of the adhesive can be obviously improved, and the bonding strength is enhanced.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
The formaldehyde-free release environment-friendly adhesive for the solid wood composite floor in the embodiment 1 is prepared from the following raw materials in percentage by mass:
the molecular weight of the polytetrahydrofuran dihydric alcohol is 2500.
Mixing polytetrahydrofuran diol, 1010, DY-20 and A151, heating to 130 ℃, and fully and uniformly mixing; MDI-100 is heated to 50 ℃; BDO is heated to 45 ℃; the heated raw materials are accurately measured and then injected into an extruder through a high-speed stirring head, the measured superfine inorganic filler-talcum powder is added into the rear section of the extruder, the mixed materials are fully reacted and plasticized in a screw rod, and the mixed materials are granulated through an underwater cutting system to obtain the final product.
Example 2
The formaldehyde-free release environment-friendly adhesive for the solid wood composite floor in the embodiment 2 is prepared from the following raw materials in percentage by mass:
the molecular weight of the polytetrahydrofuran dihydric alcohol is 2800.
The preparation process comprises the following steps: mixing polytetrahydrofuran diol, 1010, DY-20 and A151, heating to 135 ℃, and fully and uniformly mixing; MDI-100 is heated to 50 ℃; BDO is heated to 45 ℃; the heated raw materials are accurately measured and then injected into an extruder through a high-speed stirring head, the measured superfine inorganic filler-talcum powder is added into the rear section of the extruder, the mixed materials are fully reacted and plasticized in a screw rod, and the mixed materials are granulated through an underwater cutting system to obtain the final product.
Example 3
The formaldehyde-free release environment-friendly adhesive for the solid wood composite floor in the embodiment 3 is prepared from the following raw materials in percentage by mass:
the molecular weight of the polytetrahydrofuran dihydric alcohol is 3000.
The preparation process comprises the following steps: mixing polytetrahydrofuran diol, 1010, DY-20 and A151, heating to 145 ℃, and fully and uniformly mixing; MDI-100 is heated to 50 ℃; BDO is heated to 45 ℃; the heated raw materials are accurately measured and then injected into an extruder through a high-speed stirring head, the measured superfine inorganic filler-talcum powder is added into the rear section of the extruder, the mixed materials are fully reacted and plasticized in a screw rod, and the mixed materials are granulated through an underwater cutting system to obtain the final product.
Comparative example 1
The adhesive of comparative example 1 is prepared from the following raw materials in percentage by mass:
the molecular weight of the polytetrahydrofuran dihydric alcohol is 3000.
The preparation process comprises the following steps: mixing polytetrahydrofuran diol, 1010 and DY-20, heating to 145 ℃, and fully and uniformly mixing; MDI-100 is heated to 50 ℃; BDO is heated to 45 ℃; and (3) injecting the heated raw materials into an extruder through a high-speed stirring head after accurate measurement, fully reacting and plasticizing the mixed materials in a screw, and granulating by an underwater cutting system to obtain a final product.
The adhesive is detected according to the requirements of class II adhesives specified in GB/T14074, and mainly detects the appearance, the bonding strength, the curing time, the free formaldehyde content, the storage stability and the dipping stripping performance; the results are shown in table 1:
table 1 adhesive performance test tables prepared in examples 1 to 3 and comparative example 1
According to the detection data, the physical properties of the formaldehyde-free release environment-friendly adhesive for the solid wood composite floor are obviously higher than the national standard requirements, and the most important point is that no formaldehyde is released. In addition, the adhesive strength of the adhesive can be obviously improved by adding the superfine inorganic filler. The above-mentioned embodiments are preferred embodiments of the present invention, and not intended to limit the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the present invention.
Claims (6)
1. The formaldehyde-free release environment-friendly adhesive for the solid wood composite floor is characterized by comprising the following components in parts by weight: the raw materials comprise the following components in percentage by mass:
the polyether type dihydric alcohol is one or a mixture of a plurality of polyoxyethylene dihydric alcohol, polyoxypropylene dihydric alcohol, polytetrahydrofuran dihydric alcohol or vinyl polymer grafted polyether dihydric alcohol in any proportion, and the molecular weight is between 2500-3000;
the diisocyanate is one of 4,4' -diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, toluene isocyanate or phenylene-1, 4-diisocyanate;
the preparation method of the formaldehyde-free release environment-friendly adhesive for the solid wood composite floor comprises the following steps:
mixing and heating polyether type dihydric alcohol, an antioxidant, a catalyst and a coupling agent to 130-150 ℃, and fully and uniformly mixing; heating diisocyanate to 45-55 ℃, and heating the chain extender to 45-55 ℃; the heated raw materials are metered and then injected into an extruder through a high-speed stirring head, the metered superfine inorganic filler is added into the rear section of the extruder, the mixed materials are fully reacted and plasticized in a screw rod, and the formaldehyde-free release environment-friendly adhesive is obtained after granulation by an underwater cutting system.
2. The formaldehyde-free release environment-friendly adhesive for solid wood composite floors as claimed in claim 1, which is characterized in that: the chain extender is one or a mixture of more of ethylene glycol, 1, 4-butanediol, 1, 2-propanediol, 1, 3-propanediol or 2-methyl-1, 3-propanediol in any proportion.
3. The formaldehyde-free release environment-friendly adhesive for solid wood composite floors as claimed in claim 1, which is characterized in that: the antioxidant is one or more of hindered phenol antioxidant or phosphite antioxidant mixed in any proportion.
4. The formaldehyde-free release environment-friendly adhesive for solid wood composite floors as claimed in claim 1, which is characterized in that: the superfine inorganic filler is one or more of calcium carbonate, magnesium carbonate, talcum powder, titanium pigment, white carbon black or kaolin which are mixed in any proportion, and the mesh number of the superfine inorganic filler is more than or equal to 1000 meshes.
5. The formaldehyde-free release environment-friendly adhesive for solid wood composite floors as claimed in claim 1, which is characterized in that: the coupling agent is one or a mixture of more of polyolefins, polyolefin salts, alkenyl organosilanes, titanate or chromium complexes in any proportion; the catalyst is one of organic bismuth or titanate catalyst.
6. The application of the formaldehyde-free release environment-friendly adhesive for the solid wood composite floor as claimed in claim 1, is characterized in that: preparing the formaldehyde-free release environment-friendly adhesive into a hot melt adhesive sheet, placing the adhesive sheet between floor layers, and finally obtaining the solid wood composite floor through hot pressing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811155071.3A CN109181618B (en) | 2018-09-30 | 2018-09-30 | Formaldehyde-release-free environment-friendly adhesive for solid wood composite floor and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811155071.3A CN109181618B (en) | 2018-09-30 | 2018-09-30 | Formaldehyde-release-free environment-friendly adhesive for solid wood composite floor and preparation method thereof |
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| CN109181618A CN109181618A (en) | 2019-01-11 |
| CN109181618B true CN109181618B (en) | 2021-07-02 |
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| CN113667096A (en) * | 2021-09-06 | 2021-11-19 | 湖南省玛芸家居科技有限公司 | Environment-friendly MDI glue and contain its fire prevention formaldehyde-free panel for furniture |
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| CN102345366A (en) * | 2010-08-06 | 2012-02-08 | 上海昱龄环保科技有限公司 | Production process of formaldehydeless three-layer solid-wood composite floor |
| CN202509731U (en) * | 2012-03-21 | 2012-10-31 | 上海菲林格尔木业股份有限公司 | Low-formaldehyde solid wood engineered flooring |
| CN103013425A (en) * | 2012-12-27 | 2013-04-03 | 南通高盟新材料有限公司 | Adhesive for solid wood floor and preparation method thereof |
| CN105086896A (en) * | 2015-08-18 | 2015-11-25 | 吉林森工化工有限责任公司 | Urea formaldehyde resin adhesive for wood composite floor boards |
| CN107699165A (en) * | 2017-11-29 | 2018-02-16 | 广西众昌树脂有限公司 | Low formaldehyde solid wooden compound floor adhesive |
Family Cites Families (5)
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| JPS5558278A (en) * | 1978-10-26 | 1980-04-30 | Takeda Chem Ind Ltd | Two-pack urethane coating composition for elastic substrate |
| JP2675843B2 (en) * | 1988-12-22 | 1997-11-12 | 三井東圧化学株式会社 | Flexible high strength urethane binder |
| PL362645A1 (en) * | 2000-10-23 | 2004-11-02 | Henkel Kommanditgesellschaft Auf Aktien | Reactive adhesive with a low monomer content and with multistage hardening |
| CN102102005B (en) * | 2010-12-13 | 2013-06-05 | 嘉兴禾欣化学工业有限公司 | Preparation method of environmentally-friendly aqueous polyurethane adhesive |
| CN107474785A (en) * | 2017-09-14 | 2017-12-15 | 郑州华普密封材料有限公司 | The soybean oil base moisture cure urethanes adhesive for wood of environment-friendly type |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102345366A (en) * | 2010-08-06 | 2012-02-08 | 上海昱龄环保科技有限公司 | Production process of formaldehydeless three-layer solid-wood composite floor |
| CN202509731U (en) * | 2012-03-21 | 2012-10-31 | 上海菲林格尔木业股份有限公司 | Low-formaldehyde solid wood engineered flooring |
| CN103013425A (en) * | 2012-12-27 | 2013-04-03 | 南通高盟新材料有限公司 | Adhesive for solid wood floor and preparation method thereof |
| CN105086896A (en) * | 2015-08-18 | 2015-11-25 | 吉林森工化工有限责任公司 | Urea formaldehyde resin adhesive for wood composite floor boards |
| CN107699165A (en) * | 2017-11-29 | 2018-02-16 | 广西众昌树脂有限公司 | Low formaldehyde solid wooden compound floor adhesive |
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