CN102304337A - Novel environmental-friendly modified glue for impregnated paper and preparation method thereof - Google Patents
Novel environmental-friendly modified glue for impregnated paper and preparation method thereof Download PDFInfo
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- CN102304337A CN102304337A CN201110140659A CN201110140659A CN102304337A CN 102304337 A CN102304337 A CN 102304337A CN 201110140659 A CN201110140659 A CN 201110140659A CN 201110140659 A CN201110140659 A CN 201110140659A CN 102304337 A CN102304337 A CN 102304337A
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Abstract
The invention relates to novel environmental-friendly modified glue for impregnated paper and a preparation method thereof. The modified glue comprises the following raw materials in parts by weight: 40-60 parts of water, 20-26 parts of tripolycyanamide, 5-25 parts of dialdehyde, 10-25 parts of monoaldehyde, 1-5 parts of crosslinking modifying agent, 1-5 parts of auxiliary synthetic agent and 1-2 parts of post eliminating agent. The invention also provides the preparation method of the modified glue; the invention solves the problem that the traditional glue for impregnated paper has stronger smell and high free formaldehyde, also ensures every performance index and increases the hardness and the chemical property resistance.
Description
Technical field
The present invention relates to a kind of novel environment friendly impregnated paper with modified adhesive and preparation method thereof, belong to a kind of environment-friendly type macromolecule novel material.
Background technology
On most of furniture of China and the composite floor board market, be main with melamine glue impregnated paper veneer technology how, its product color is clear, and glossiness is good, and hardness is high, and chemical resistance is excellent, is to use the most extensive and reliable technology on the present domestic and international market.But in the pollution that melamine glue is processed in the process and the dipping link can produce workman and surrounding enviroment; In addition along with Copenhagen meeting world low-carbon economy development megatrend; Increasing Chemical Manufacture details is much accounted of, and many enterprises require strict more to processing control simultaneously.At present, domestic impregnated paper manufacturing enterprise is many is that main raw material(s) carries out impregnation with the melamine glue.The process of producing and process melamine glue has a large amount of free formaldehydes to be discharged in the environment, and enterprise product and self-growth have been caused influence.So gum dipped paper production and processing producer, solve the technology barriers that the free formaldehyde problem becomes its industry.
Summary of the invention
The present invention seeks to solve above-mentioned traditional impregnated paper glue; Smell is heavy, free formaldehyde is high, environment is caused the severe contamination problem; A kind of novel environment friendly impregnated paper modified adhesive is provided; This product has not only solved traditional impregnated paper with the high problem of the free formaldehyde of glue; Also guarantee each item performance index, improved hardness and chemical resistance.
The technical scheme that the present invention adopts is:
A kind of novel environment friendly impregnated paper modified adhesive, it is characterized in that: the raw material of said modified adhesive and raw materials in part by weight are:
Water: 40-60 part; Trimeric cyanamide: 20-26 part; Dialdehyde: 5-25 part; Monoaldehyde: 10-25 part; Cross-linked modifier: 1-5 part; Help compound agent: 1-5 part, back remover: 1-2 part.
Preferably, described monoaldehyde is one or more mixtures in formaldehyde, acetaldehyde, the butyraldehyde.
Preferably, described dialdehyde is one or both in glutaraldehyde, the hexanedial.
Preferably, described cross-linked modifier is hexanolactam, acrylamide, N, one or more mixtures in the inferior acid amides of the two methyl of N-, the N methacrylamide.
Preferably, the described compound agent that helps is in Diethylene Glycol, the triglycol one or both.
Preferably, described back remover is a hydrogen peroxide, ammonium persulphate, one or more mixtures in the tertbutyl peroxide.
The present invention also provides the preparation method of above-mentioned modified adhesive, comprises the steps:
(1) water and monoaldehyde are added reaction kettle according to the above ratio; Water is 40-60 part; Monoaldehyde is 10-25 part; Add the pH regulator agent again and carry out the pH value and be adjusted to 9-10, be warming up to 40 degree, again dialdehyde is added according to the above ratio; Dialdehyde is 5-25 part; Be warming up to the 60-90 degree again, add the pH regulator agent again, accent PH is 9-10.
(2) 6-8 part trimeric cyanamide is added reaction kettle; Fully reaction saw in 20 minutes solution limpid after; Add again 6-8 part trimeric cyanamide react saw in 20 minutes solution limpid after, add 8-10 part trimeric cyanamide again and react, trimeric cyanamide three times accumulative total add-on is 20-26 part.
(3) etc. in the reaction kettle behind the solution transparent and homogeneous, add cross-linked modifier 1-5 part and help compound agent 1-5 part, add back remover 1-2 part, vacuumize and eliminate free aldehyde in the reaction kettle in the reaction later stage.
(4) cooling is filtered discharging below 50 ℃.
Described pH regulator agent is sodium hydroxide, ammoniacal liquor, one or more mixtures of trolamine.
What the present invention adopted is environment-friendly type aqueous melamine resin, can in polymerization process, adopt semi-continuous charging method and crosslinking technological, with superpolymer carry out adding cross-linked modifier after the modification, help compound agent, back remover etc. is processed modified adhesive.Reaction mechanism of the present invention is following:
1. trimeric cyanamide and monoaldehyde reaction:
2. trimeric cyanamide and dialdehyde reaction:
3. reaction intermediate and linking agent reaction:
4. the partial reaction of dialdehyde in system:
Further reaction generates tridimensional network with the methylol reaction of monoaldehyde.
The beneficial effect that the present invention had:
1, traditional melamine glue is mainly by trimeric cyanamide and formaldehyde effect; The introducing of dialdehyde has reduced the especially usage quantity of formaldehyde of monoaldehyde among the present invention; And promoted polycondensation; Reaction few remaining aldehyde of later stage again through vacuumize and oxidizing reaction such as back remover in from system, remove; Use the trimeric cyanamide or the urea-formaldehyde glue of this kind method that the system burst size of methanal is reduced greatly, pollution-free to atmosphere.
2, the present invention adds linking agent in reaction process has more cross-linking set by macromolecular chain segment, for the later stage overlays to solidify good film-forming properties is provided.
3, the present invention adopts semicontinuous feeding method in reaction process, allow early stage aldehyde radical excessive with trimeric cyanamide reaction, it is more abundant that substep adds trimeric cyanamide polycondensation stage by stage.
4, the present invention adds the back remover in the reaction later stage, makes in the polycondensation not the aldehydes monomer of complete reaction enter into macromolecular chain segment and participates in reaction.
Embodiment
Below in conjunction with specific embodiment the present invention is described further.
Embodiment 1
A kind of novel environment friendly impregnated paper comprises the steps: with the preparation method of modified adhesive
1. water and formaldehyde are added reaction kettle in proportion, 55 parts of water, 22 parts of formaldehyde add sodium hydroxide again and carry out the pH value and be adjusted to 9.5, are warming up to 40 degree, 5 parts of glutaraldehyde are added again, and are warming up to 78 degree again, add ammoniacal liquor again, and transferring pH is 9.5.
2. 6 parts of trimeric cyanamides are added reaction kettle in proportion; Fully reaction saw in 20 minutes solution limpid after; Add again 6 parts of trimeric cyanamides react saw in 20 minutes solution limpid after, add 8 parts of trimeric cyanamides again and react, trimeric cyanamide three times accumulative total add-on is 20 parts.
3. wait in the reaction kettle behind the solution transparent and homogeneous, add 2.3 parts of cross-linked modifier hexanolactams and help 3.1 parts of compound agent triglycols.Add 1.6 parts of back remover ammonium persulphates in the reaction later stage, vacuumize and eliminate free aldehyde in the reaction kettle.
4. lower the temperature below 50 ℃, filter discharging, get the modified adhesive finished product.
Embodiment 2
A kind of novel environment friendly impregnated paper comprises the steps: with the preparation method of modified adhesive
1. water and acetaldehyde are added reaction kettle in proportion, 50 parts of water, 23 parts of acetaldehyde add sodium hydroxide again and carry out the pH value and be adjusted to 10, are warming up to 40 degree, 7.5 parts of hexanedials are added in proportion again, are warming up to 81 degree again, add sodium hydroxide solution again, and transferring PH is 10.
2. 7 parts of trimeric cyanamides are added reaction kettle in proportion; Fully reaction saw in 20 minutes solution limpid after; Add again 7 parts of trimeric cyanamides react saw in 20 minutes solution limpid after, add 10 parts of trimeric cyanamides again and react, trimeric cyanamide three times accumulative total add-on is 24 parts.
3. wait in the reaction kettle behind the solution transparent and homogeneous, add 3.8 parts of cross-linked modifier acrylamides and help 1.2 parts of compound agent Diethylene Glycols.Add 1.5 parts of back remover tertbutyl peroxides in the reaction later stage, vacuumize and eliminate free aldehyde in the reaction kettle.
4. lower the temperature below 50 ℃, filter discharging, get the modified adhesive finished product.
The above only is preferred embodiment of the present invention, is not technical scheme of the present invention is done any pro forma restriction.Every foundation technical spirit of the present invention all still belongs in the scope of technical scheme of the present invention any simple modification, equivalent variations and modification that above embodiment did.
Claims (8)
1. novel environment friendly impregnated paper modified adhesive, it is characterized in that: the raw material of said modified adhesive and raw materials in part by weight are: water: 40-60 part; Trimeric cyanamide: 20-26 part; Dialdehyde: 5-25 part; Monoaldehyde: 10-25 part; Cross-linked modifier: 1-5 part; Help compound agent: 1-5 part, back remover: 1-2 part.
2. a kind of novel environment friendly impregnated paper modified adhesive according to claim 1 is characterized in that: described monoaldehyde is one or more mixtures in formaldehyde, acetaldehyde, the butyraldehyde.
3. a kind of novel environment friendly impregnated paper modified adhesive according to claim 1 and 2, it is characterized in that: described dialdehyde is one or both in glutaraldehyde, the hexanedial.
4. according to each described a kind of novel environment friendly impregnated paper modified adhesive of claim 1-3; It is characterized in that: described cross-linked modifier is hexanolactam, acrylamide, N, one or more mixtures in the inferior acid amides of the two methyl of N-, the N methacrylamide.
5. according to each described a kind of novel environment friendly impregnated paper modified adhesive of claim 1-4, it is characterized in that: the described compound agent that helps is in Diethylene Glycol, the triglycol one or both.
6. according to each described a kind of novel environment friendly impregnated paper modified adhesive of claim 1-5, it is characterized in that: described back remover is a hydrogen peroxide, ammonium persulphate, one or more mixtures in the tertbutyl peroxide.
7. the preparation method of each said modified adhesive of claim 1-6 is characterized in that: comprise the steps:
(1) water and monoaldehyde are added reaction kettle according to the above ratio; Water is 40-60 part; Monoaldehyde is 10-25 part; Add the pH regulator agent again and carry out the pH value and be adjusted to 9-10, be warming up to 40 degree, again dialdehyde is added according to the above ratio; Dialdehyde is 5-25 part; Be warming up to the 60-90 degree again, add the pH regulator agent again, accent PH is 9-10;
(2) 6-8 part trimeric cyanamide is added reaction kettle; Fully reaction saw in 20 minutes solution limpid after; Add again 6-8 part trimeric cyanamide react saw in 20 minutes solution limpid after, add 8-10 part trimeric cyanamide again and react, trimeric cyanamide three times accumulative total add-on is 20-26 part;
(3) etc. in the reaction kettle behind the solution transparent and homogeneous, add cross-linked modifier 1-5 part and help compound agent 1-5 part, add back remover 1-2 part, vacuumize and eliminate free aldehyde in the reaction kettle in the reaction later stage;
(4) cooling is filtered discharging below 50 ℃.
8. according to the preparation method of the said modified adhesive of claim 7, it is characterized in that:
Described pH regulator agent is sodium hydroxide, ammoniacal liquor, one or more mixtures of trolamine.
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| CN201110140659.3A CN102304337B (en) | 2011-05-27 | 2011-05-27 | Novel environmental-friendly modified glue for impregnated paper and preparation method thereof |
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| CN201110140659.3A CN102304337B (en) | 2011-05-27 | 2011-05-27 | Novel environmental-friendly modified glue for impregnated paper and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015032458A1 (en) * | 2013-09-04 | 2015-03-12 | Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. | Wood product or natural fiber composite material product and use of a formaldehyde-free aminoplast resin for the production thereof |
| WO2015032733A1 (en) * | 2013-09-04 | 2015-03-12 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. | Formaldehyde-free amino or amide resins based on a reactive protective group and a di- or trialdehyde as a crosslinking agent |
| CN104497938A (en) * | 2014-12-01 | 2015-04-08 | 中山冠华竹纤板业有限公司 | Modified bamboo fiber board adhesive and production method thereof |
| CN105887557A (en) * | 2014-12-24 | 2016-08-24 | 天津元鸿科技有限公司 | Novel environmental protection impregnated paper |
| CN108687887A (en) * | 2018-04-23 | 2018-10-23 | 太尔化工（南京）有限公司 | A kind of preparation method and application of solid-state bloom melamine-impregnated decorative paper |
| CN109468876A (en) * | 2018-10-22 | 2019-03-15 | 天津市盛世德新材料科技有限公司 | Abrasion-proof paper and its manufacturing method |
| CN114108365A (en) * | 2021-12-06 | 2022-03-01 | 东莞市高益装饰材料有限公司 | Melamine softening coated paper and production process thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5691426A (en) * | 1994-12-07 | 1997-11-25 | Sequa Chemicals, Inc. | Resin composition |
| CN101265314A (en) * | 2008-04-30 | 2008-09-17 | 北京化工大学 | Environmental protection urea-formaldehyde resin and preparation method thereof |
-
2011
- 2011-05-27 CN CN201110140659.3A patent/CN102304337B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5691426A (en) * | 1994-12-07 | 1997-11-25 | Sequa Chemicals, Inc. | Resin composition |
| CN101265314A (en) * | 2008-04-30 | 2008-09-17 | 北京化工大学 | Environmental protection urea-formaldehyde resin and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 何乃叶: "《低压短周期浸渍用三聚氰胺甲醛树脂改性研究》", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
| 李陶琦等: "《低游离甲醛三聚氰胺甲醛树脂的合成》", 《应用化学》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015032458A1 (en) * | 2013-09-04 | 2015-03-12 | Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. | Wood product or natural fiber composite material product and use of a formaldehyde-free aminoplast resin for the production thereof |
| WO2015032733A1 (en) * | 2013-09-04 | 2015-03-12 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. | Formaldehyde-free amino or amide resins based on a reactive protective group and a di- or trialdehyde as a crosslinking agent |
| DE102013014641B4 (en) | 2013-09-04 | 2018-07-12 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Wood product or natural fiber composite product and use of a formaldehyde-free aminoplast resin for their preparation |
| CN104497938A (en) * | 2014-12-01 | 2015-04-08 | 中山冠华竹纤板业有限公司 | Modified bamboo fiber board adhesive and production method thereof |
| CN105887557A (en) * | 2014-12-24 | 2016-08-24 | 天津元鸿科技有限公司 | Novel environmental protection impregnated paper |
| CN108687887A (en) * | 2018-04-23 | 2018-10-23 | 太尔化工（南京）有限公司 | A kind of preparation method and application of solid-state bloom melamine-impregnated decorative paper |
| CN109468876A (en) * | 2018-10-22 | 2019-03-15 | 天津市盛世德新材料科技有限公司 | Abrasion-proof paper and its manufacturing method |
| CN114108365A (en) * | 2021-12-06 | 2022-03-01 | 东莞市高益装饰材料有限公司 | Melamine softening coated paper and production process thereof |
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| CN102304337B (en) | 2015-04-08 |
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Effective date of registration: 20150518 Address after: 300382 Tianjin city Xiqing District Jingwu Town Xin Valley Road No. 1 Patentee after: Tianjin spirit decoration new Mstar Technology Ltd Address before: 300382 Tianjin Segotep Technology Park Xiqing District Jingwu town Segotep Road No. 6 Patentee before: Tianjin Xinyuan Senda New Material Technology Co., Ltd. |
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Address after: 300382 Tianjin city Xiqing District Jingwu Town Xin Valley Road No. 1 Patentee after: Tianjin Shengshi new Mstar Technology Ltd Address before: 300382 Tianjin city Xiqing District Jingwu Town Xin Valley Road No. 1 Patentee before: Tianjin spirit decoration new Mstar Technology Ltd |