CN108587539A - The preparation method of glucose modified melamine formaldehyde resin wood adhesive - Google Patents
The preparation method of glucose modified melamine formaldehyde resin wood adhesive Download PDFInfo
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- CN108587539A CN108587539A CN201810369951.4A CN201810369951A CN108587539A CN 108587539 A CN108587539 A CN 108587539A CN 201810369951 A CN201810369951 A CN 201810369951A CN 108587539 A CN108587539 A CN 108587539A
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- glucose
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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
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09J161/32—Modified amine-aldehyde condensates
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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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
Abstract
The invention discloses a kind of glucose modified melamine resin wood adhesives (GMF resins) of Optimal improvements, and as raw material and stabilizer mainly is added using glucose, melamine and formaldehyde, is made up of methylolation and polycondensation reaction.Wherein, glucose is added in formalin simultaneously with melamine, so that it is participated in the entire reaction process of resin, and be finally warming up to 85 DEG C.Preparation method of the present invention is simple, and gained GMF wood adhesives are compared with traditional MF resins, and stability is good, storage period is longer, and resin brittleness is improved, and color and luster is good with timber compatibility, is suitable for the production requirement of timber industry.
Description
Technical field
Wood-based Panel Production and polymeric material field in being processed the invention belongs to timber, more particularly to it is a kind of glucose modified
The preparation method of melamine formaldehyde resin wood adhesive.
Background technology
With the variation of wood raw material structure, China's wood materials supply by traditional based on solid wood turn to
It is glued based on wood materials, present woodwork majority is processed by wood-based plate.The development of wood-based panel industry greatly carries
The high market demand of wood adhesive, the technological progress of wood adhesive are the important bases of industry of artificial boards development.
Currently, UF resins still occupy leading (accounting for about 90%) (containing being modified) in adhesive needed for China's Wood-based Panel Production, but
In contrast, MF resins show higher resistance to ability of endurance boiling water, this is because solubility is very low in water for melamine, and have
There is the cyclic structure triazine ring of good thermal stability.The presence of this rigid radical, but also hardness is big, crisp after MF resin solidifications
Property it is high, almost without toughness.In addition, in the presence of bases such as the hydroxyl (- OH) of stronger reactivity, imino groups (- NH-) in MF resins
Group, persistently crosslinks reaction, easily leads to gel, storage stability is bad.Therefore, modification appropriate is carried out to MF resins, expanded
It is imperative to improve using effect for big application range.
In recent years, starch conversion technology continues to develop, (the synthesis of tapioca base environment-friendly type wood adhesive such as sweet satellite
Study (I) --- formulation optimization [J] the Sino-South African Forestry University of Science and Technology journal based on uniform design, 2011,31 (09)：128-132
+ 174) using tapioca, melamine, formaldehyde as raw material, then it is aided with crosslinking agent and has synthesized a kind of tapioca base environment-friendly type wood
Material adhesive simultaneously determines adhesive optimum synthesis condition.
Glucose is the product of starch complete hydrolysis, is derived from a wealth of sources.(the glucose-melamine-formaldehyde copolymerization such as Lv Jingbo
Resins synthesis and performance study [J] forest product industrys, 2016,43 (07)：15-18+35) have studied under alkaline condition, glucose,
The copolyreaction of melamine and formaldehyde.Preparation method is after formaldehyde first carries out addition reaction with melamine, to add Portugal
Grape sugar copolycondensation, is warming up to 88 DEG C, after reaction to after determining water tolerance, you can blanking.The experimental results showed that：GMF resins are excellent
Technique is combined to as 88 DEG C of synthesis reaction temperature, the molar ratio 0.1~0.4 of pH value 9.0~9.5, glucose and melamine, storage
(25 DEG C) are deposited the phase up to 9~15d.
Invention content
The technical problem to be solved in the present invention is to provide a kind of glucose modified melamines simple for process, of good performance
The preparation method of amine-formaldehyde resin wood adhesive.
In order to solve the above technical problems, the present invention uses following technical scheme：
Glucose modified melamine formaldehyde resin wood adhesive is mainly original with glucose, melamine and formaldehyde
Expect and be added stabilizer, is made up of methylolation and polycondensation reaction.Wherein, glucose is added to formaldehyde simultaneously with melamine
In solution, it is set to participate in the entire reaction process of resin, and be finally warming up to 85 DEG C.
The mass ratio of glucose and melamine is 0.14~0.71: 1, and the molar ratio of formaldehyde and melamine is 2.0: 1,
Stabilizer accounts for the 17.45%~23.22% of adhesive total amount, and the theoretical solids content of resin is 55% after stabilizer addition.
Stabilizer is one or more of ethyl alcohol, first alcohol and water.
The adhesive is light yellow clear liquid, and solid content is that 50~55%, pH is 8.0~8.5, water tolerance (25
DEG C) it is 2.5~3.0 times of water, storage period is 15~20 days, and bonding strength >=0.7MPa reaches national " I " class glued board standard.
The preparation method of above-mentioned glucose modified melamine formaldehyde resin wood adhesive, includes the following steps：
(1) 90.09 parts by weight paraformaldehydes and 153.40 parts by weight distilled water are added in four-hole boiling flask, are protected with aqueous slkali
Hold pH value be 9.0, stir and heat mass fraction be 37% clarification formalin；
(2) stirring is lower while 189.18 parts by weight melamines and 27.01~108.04 parts by weight glucose are added, heating
To 80 DEG C, 40min is kept the temperature, it is 9.0 to keep pH value with aqueous slkali；
(3) be warming up to 85 DEG C, after keeping the temperature 60min, measure resin water tolerance (25 DEG C), when water tolerance reaches 2.5~
When 3.0 times of water, 97.19~163.49 parts by weight stabilizer letdown resin solid contents are added to 55%, pH is adjusted with aqueous slkali
To 8.5~9.0, be cooled to 40 DEG C or less blowings to get.
The aqueous slkali for adjusting pH value is one or both of the sodium hydroxide solution of mass fraction 30%, ammonium hydroxide.Heating
Speed is 4 DEG C/5min.
The present invention is on the original Research foundation of Lv Jing waves, after further study, has developed a kind of glucose of Optimal improvements
Modified cyanurotriamide-formaldehyde resin wood adhesive (GMF resins), mainly using glucose, melamine and formaldehyde as raw material simultaneously
Stabilizer is added, is made up of methylolation and polycondensation reaction.Wherein, glucose is added to formalin simultaneously with melamine
In, so that it is participated in the entire reaction process of resin, and be finally warming up to 85 DEG C.Gained GMF resins of the invention, relatively before storage
Phase extends 2~10 days, and ensure that bonding strength.This may be the addition in advance due to glucose, make its more fully with
The mode of chemical bonding participates in resin system, reduces resin crosslink density, reduces in resin system between active group
Interaction；The reduction of condensation temperature not only reduces energy consumption, but also promotes the cross-linking reaction of resin more gentle, avoids shape
At the non-uniform macromolecular chain of molecular weight, the bin stability of GMF resins is then further enhanced.Meanwhile prepared by the present invention
Method is simple, and gained GMF wood adhesives are compared with traditional MF resins, and stability is good, storage period is longer, and resin brittleness obtains
To improvement, color and luster is good with timber compatibility, is suitable for the production requirement of timber industry.
Specific implementation mode
Embodiment 1
Raw material proportioning：The mass ratio of glucose and melamine is 0.14: 1, and the molar ratio of formaldehyde and melamine is 2.0
: 1, stabilizer accounts for the 17.45% of adhesive total amount, and the theoretical solids content of resin is 55%.
Preparation method：
(1) 90.09 parts by weight paraformaldehydes and 153.40 parts by weight distilled water are added in four-hole boiling flask, use aqueous slkali
(mass fraction be 30% sodium hydroxide solution, similarly hereinafter) keep pH value be 9.0, stir and heat (heating rate be 4 DEG C/
5min, similarly hereinafter) obtain the clarification formalin that mass fraction is 37%；
(2) 189.18 parts by weight melamines and 27.01 parts by weight glucose are sequentially added under stirring, are warming up to 80 DEG C,
40min is kept the temperature, it is 9.0 to keep pH value with aqueous slkali；
(3) be warming up to 85 DEG C, after keeping the temperature 60min, measure resin water tolerance (25 DEG C), when water tolerance reaches 2.5~
When 3.0 times of water, 97.19 parts by weight stabilizers (water, similarly hereinafter) letdown resin solid content is added to 55%, pH is adjusted with aqueous slkali
To 8.5~9.0, be cooled to 40 DEG C or less blowings to get.
Properties of product：Adhesive is light yellow clear liquid, and theoretical solids content 55%, pH is 8.5~9.0, molten water
(25 DEG C) of multiple is 2.5~3.0 times of water, and storage period is 20 days (compared to M in above-mentioned Lv Jing waves articleg/MmStorage period when=0.1
Extend 10 days), bonding strength >=0.7MPa, prepared glued board reaches national " I " class glued board standard.
Embodiment 2
Raw material proportioning：The mass ratio of glucose and melamine is 0.29: 1, and the molar ratio of formaldehyde and melamine is 2.0
: 1, stabilizer accounts for the 19.69% of adhesive total amount, and the theoretical solids content of resin is 55%.
Preparation method：
(1) 90.09 parts by weight paraformaldehydes and 153.40 parts by weight distilled water are added in four-hole boiling flask, use aqueous slkali
(mass fraction be 30% sodium hydroxide solution, similarly hereinafter) keep pH value be 9.0, stir and heat (heating rate be 4 DEG C/
5min, similarly hereinafter) obtain the clarification formalin that mass fraction is 37%；
(2) 189.18 parts by weight melamines and 54.02 parts by weight glucose are sequentially added under stirring, are warming up to 80 DEG C,
40min is kept the temperature, it is 9.0 to keep pH value with aqueous slkali；
(3) be warming up to 85 DEG C, after keeping the temperature 60min, measure resin water tolerance (25 DEG C), when water tolerance reaches 2.5~
When 3.0 times of water, 119.29 parts by weight stabilizers (water, similarly hereinafter) letdown resin solid content is added and, to 55%, is adjusted with aqueous slkali
PH to 8.5~9.0, be cooled to 40 DEG C or less blowings to get.
Properties of product：Adhesive is light yellow clear liquid, and theoretical solids content 55%, pH is 8.5~9.0, molten water
(25 DEG C) of multiple is 2.5~3.0 times of water, and storage period is 18 days (compared to M in above-mentioned Lv Jing waves articleg/MmStorage period when=0.2
Extend 6 days), bonding strength >=0.7MPa, prepared glued board reaches national " I " class glued board standard.
Embodiment 3
Raw material proportioning：The mass ratio of glucose and melamine is 0.43: 1, and the molar ratio of formaldehyde and melamine is 2.0
: 1, stabilizer accounts for the 21.58% of adhesive total amount, and the theoretical solids content of resin is 55%.
Preparation method：
(1) 90.09 parts by weight paraformaldehydes and 153.40 parts by weight distilled water are added in four-hole boiling flask, use aqueous slkali
(mass fraction be 30% sodium hydroxide solution, similarly hereinafter) keep pH value be 9.0, stir and heat (heating rate be 4 DEG C/
5min, similarly hereinafter) obtain the clarification formalin that mass fraction is 37%；
(2) 189.18 parts by weight melamines and 81.03 parts by weight glucose are sequentially added under stirring, are warming up to 80 DEG C,
40min is kept the temperature, it is 9.0 to keep pH value with aqueous slkali；
(3) be warming up to 85 DEG C, after keeping the temperature 60min, measure resin water tolerance (25 DEG C), when water tolerance reaches 2.5~
When 3.0 times of water, 141.39 parts by weight stabilizers (water, similarly hereinafter) letdown resin solid content is added and, to 55%, is adjusted with aqueous slkali
PH to 8.5~9.0, be cooled to 40 DEG C or less blowings to get.
Properties of product：Adhesive is light yellow clear liquid, and theoretical solids content 55%, pH is 8.5~9.0, molten water
(25 DEG C) of multiple is 2.5~3.0 times of water, and storage period is 17 days (compared to M in above-mentioned Lv Jing waves articleg/MmStorage period when=0.3
Extend 2 days), bonding strength >=0.7MPa, prepared glued board reaches national " I " class glued board standard.
Embodiment 4
Raw material proportioning：The mass ratio of glucose and melamine is 0.71: 1, and the molar ratio of formaldehyde and melamine is 2.0
: 1, stabilizer accounts for the 23.22% of adhesive total amount, and the theoretical solids content of resin is 55%.
Preparation method：
(1) 90.09 parts by weight paraformaldehydes and 153.40 parts by weight distilled water are added in four-hole boiling flask, use aqueous slkali
(mass fraction be 30% sodium hydroxide solution, similarly hereinafter) keep pH value be 9.0, stir and heat (heating rate be 4 DEG C/
5min, similarly hereinafter) obtain the clarification formalin that mass fraction is 37%；
(2) 189.18 parts by weight melamines and 108.04 parts by weight glucose are sequentially added under stirring, are warming up to 80 DEG C,
40min is kept the temperature, it is 9.0 to keep pH value with aqueous slkali；
(3) be warming up to 85 DEG C, after keeping the temperature 60min, measure resin water tolerance (25 DEG C), when water tolerance reaches 2.5~
When 3.0 times of water, 163.49 parts by weight stabilizers (water, similarly hereinafter) letdown resin solid content is added and, to 55%, is adjusted with aqueous slkali
PH to 8.5~9.0, be cooled to 40 DEG C or less blowings to get.
Properties of product：Adhesive is light yellow clear liquid, and theoretical solids content 55%, pH is 8.5~9.0, molten water
(25 DEG C) of multiple is 2.5~3.0 times of water, and storage period is 15 days (compared to M in above-mentioned Lv Jing waves articleg/MmStorage period when=0.4
Extend 6 days), bonding strength >=0.7MPa, prepared glued board reaches national " I " class glued board standard.
Claims (7)
1. a kind of glucose modified melamine formaldehyde resin wood adhesive, is mainly with glucose, melamine and formaldehyde
Simultaneously stabilizer is added in raw material, is made up of methylolation and polycondensation reaction, it is characterised in that：The glucose and melamine are same
When be added in formalin, so that it is participated in the entire reaction process of resin, and be finally warming up to 85 DEG C.
2. glucose modified melamine formaldehyde resin wood adhesive according to claim 1, it is characterised in that：Institute
The mass ratio for stating glucose and melamine is 0.14~0.71: 1, and the molar ratio of formaldehyde and melamine is 2.0: 1, stabilizer
Account for the 17.45%~23.22% of adhesive total amount.
3. glucose modified melamine formaldehyde resin wood adhesive according to claim 1, it is characterised in that：Institute
It is one or more of ethyl alcohol, first alcohol and water to state stabilizer.
4. glucose modified melamine formaldehyde resin wood adhesive according to claim 2, it is characterised in that the glue
Stick is light yellow clear liquid, and solid content is that 50~55%, pH is 8.0~8.5, and water tolerance is 2.5~3.0 times of water,
Storage period is 15~20 days, bonding strength >=0.7MPa.
5. the preparation method of glucose modified melamine formaldehyde resin wood adhesive described in claim 1, it is characterised in that
Include the following steps：
(1) 90.09 parts by weight paraformaldehydes and 153.40 parts by weight distilled water are added in four-hole boiling flask, pH is kept with aqueous slkali
Value be 9.0, stir and heat mass fraction be 37% clarification formalin；
(2) stirring is lower while 189.18 parts by weight melamines and 27.01~108.04 parts by weight glucose are added, and is warming up to 80
DEG C, 40min is kept the temperature, it is 9.0 to keep pH value with aqueous slkali；
(3) 85 DEG C are warming up to, after keeping the temperature 60min, measures resin water tolerance, when water tolerance reaches 2.5~3.0 times of water,
97.19~163.49 parts by weight stabilizer letdown resin solid contents are added to 55%, pH to 8.5~9.0 is adjusted with aqueous slkali,
Be cooled to 40 DEG C or less blowings to get.
6. the preparation method of glucose modified melamine formaldehyde resin wood adhesive according to claim 5, special
Sign is：The aqueous slkali for adjusting pH value is one or both of the sodium hydroxide solution of mass fraction 30%, ammonium hydroxide.
7. the preparation method of glucose modified melamine formaldehyde resin wood adhesive according to claim 5, special
Sign is：The heating rate is 4 DEG C/5min.
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| CN201810369951.4A CN108587539A (en) | 2018-04-23 | 2018-04-23 | The preparation method of glucose modified melamine formaldehyde resin wood adhesive |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109439244A (en) * | 2018-10-30 | 2019-03-08 | 广西大学 | Sodium lignin sulfonate-melamine-formaldehyde copolymer resins wood adhesive and preparation method thereof |
| CN109782275A (en) * | 2019-03-14 | 2019-05-21 | 中国电建集团成都勘测设计研究院有限公司 | The reference point check system and method for GNSS deformation monitoring |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109439244A (en) * | 2018-10-30 | 2019-03-08 | 广西大学 | Sodium lignin sulfonate-melamine-formaldehyde copolymer resins wood adhesive and preparation method thereof |
| CN109782275A (en) * | 2019-03-14 | 2019-05-21 | 中国电建集团成都勘测设计研究院有限公司 | The reference point check system and method for GNSS deformation monitoring |
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Application publication date: 20180928 |