CN105440971B - A kind of curing agent of laminated wood adhesive - Google Patents
A kind of curing agent of laminated wood adhesive Download PDFInfo
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- CN105440971B CN105440971B CN201510857056.3A CN201510857056A CN105440971B CN 105440971 B CN105440971 B CN 105440971B CN 201510857056 A CN201510857056 A CN 201510857056A CN 105440971 B CN105440971 B CN 105440971B
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- Prior art keywords
- curing agent
- earth metal
- metal hydroxide
- paraformaldehyde
- adhesive
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Classifications
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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
- 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
-
- 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
- C09J11/08—Macromolecular additives
-
- 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
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09J161/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
Abstract
The present invention relates to a kind of curing agent of laminated wood adhesive, belong to field of adhesive technology.The component of the curing agent includes nano alkaline-earth metal hydroxide, and the average grain diameter of the nano alkaline-earth metal hydroxide is no more than 300nm；The nano alkaline-earth metal hydroxide accounts for 20 80wt% of curing agent.Nano alkaline-earth metal hydroxide is a kind of active principle of curing agent, can replace part paraformaldehyde, make adhesive solidification effect good, and wood adhesion intensity is high, and free formaldehyde release is low, good weatherability.
Description
Technical field
The present invention relates to a kind of curing agent of laminated wood adhesive, belong to field of adhesive technology.
Background technology
Structure laminated wood with adhesive be for structure gluing wood glue close binding agent.Structure laminated wood because component is big,
Outdoor application, structural stress can be born, therefore structure laminated wood requires that bonding strength is high with adhesive, glued temperature is low, weather-proof
Property is good, and higher intensity can be particularly kept under the extreme case such as moist, cold and hot.
The matrix resin both at home and abroad for structure gluing wood adhesive is mainly resorcinol phenol formaldehyde resin at present
And polyurethane, by adding suitable curing agent and filler, realize the bonding of laminated wood, the evaluation index master of Adhensive performance
To include bonding strength and weatherability, when particularly gluing is used for outdoor laminated wood, wind and frost sleet need to be subjected to.In order to ensure glue
The safe handling of wood is closed, influence of the outdoor environment to its glue performance must be determined.
In order to accelerate solidification rate, promote resin to be fully cured, a certain amount of curing agent need to be added in resin adhesive.
At present, there are the organic matters such as paraformaldehyde, carboxylic acids, hexamethylenetetramine and melamine with more curing agent.It is domestic
Outer researchers are in curing agent to the solidification temperature of adhesive, hardening time, wearability and glue performance etc.
Numerous studies have been carried out, it is found that curing agent significantly affects on the performance of adhesive, property that should be according to adhesive and use
The suitable curing agent of the selections such as condition.
Luo Wenshi etc.（Timber industry, 1990,4（3）：14-19）Resorcinol phenol formaldehyde resin is prepared for, using more
Polyformaldehyde solidifies, and have studied viscosity, glue temperature after curing agent adds and changes with time, gel time variation with temperature,
Filler is done using wood powder, has inquired into the relation of filling adding amount and resin viscosity, have studied preservative be added into it is right after adhesive
The influence of glue performance, by being tested to Douglas-fir is glued, it is between 6.3MPa. has found to obtain cold curing gluing intensity
The phenolic resin of the sourer solidification of laminated wood weather resistance of benzenediol-phenol-formaldehyde resin adhesive producing is good.
Wang Chunpeng etc.（Chemistry of forest product and industry, 1999,19（4）：23-28）Paraformaldehyde content be have studied to homemade
The influence of benzenediol-phenol-formaldehyde resin adhesive glue performance, the results showed that effect when adding 15% paraformaldehyde solidification
It is best.
Chen Ruixiang etc.（Forest product industry, 2002,29（2）：16-18）It has studied the different amounts of different curing agent and curing agent
To phenolic resin curing time and glue performance（MOR, internal bond strength, expansion rate etc.）Influence, the results showed that solidification
Glue performance is best when agent N addition is 4%.
Tan Jiading etc.（Journal of Chemical Industry and Engineering, 2011,62（6）：1723-1729）Inquire into, several amines such as isophorone diamine
Curing agent is to epoxy resin cure behavior and the influence of condensate performance.Result of study shows and aliphatic firming agent polyetheramine phase
Than, it is high using alicyclic curing agent isophorone diamine activity, the epoxy resin cured product of solidification have simultaneously high intensity and
High tenacity.
The content of the invention
Present invention solves the technical problem that it is to change current resorcinol phenol formaldehyde resin to use single paraformaldehyde
The shortcomings that burst size of methanal is big in solidification process and during lumber product use, a kind of cold curing, resistance to is provided for market
Water good weatherability, cementing strength be high, suitable for the curing agent of structure laminated wood adhesive.
The technical scheme is that, there is provided a kind of curing agent of laminated wood adhesive, the component bag of the curing agent
Nano alkaline-earth metal hydroxide is included, the average grain diameter of the nano alkaline-earth metal hydroxide is no more than 300nm；It is described to receive
Rice alkaline earth metal hydroxide accounts for the 20-80wt% of curing agent.
Further, the component of the curing agent includes paraformaldehyde.
Further, the content of paraformaldehyde is 30-70wt% in the curing agent.
Further, the curing agent is 1 by mass ratio:2 nano alkaline-earth metal hydroxide and paraformaldehyde composition.
Further, the component of the curing agent includes hexamethylenetetramine.
Further, the content of hexamethylenetetramine is 10-40wt% in the curing agent.
Further, the average grain diameter of the nano alkaline-earth metal hydroxide is 60-200nm.
Further, the nano alkaline-earth metal hydroxide is nano-sized magnesium hydroxide and/or nano calcium hydroxide.
The present invention further provides a kind of adhesive, and its component includes above-mentioned curing agent.
Further, the component of the adhesive includes matrix resin and filler, and curing agent accounts for the 2- of adhesive
20wt%。
Further, the resin matrix is resorcinol phenol formaldehyde resin.
Further, the filler is the one or more in wood fibre, bean powder, starch.
The nano alkaline-earth metal hydroxide of the present invention can use commercially available prod, the grain prepared using reverse microemulsion process
Footpath more conforms to require, effect is more preferable, and reverse microemulsion process is specifically：Disperse alkaline-earth metal saline solution with ethanol, in machinery
Under stirring condition, a certain amount of concentrated ammonia liquor is slowly added dropwise into three-necked flask with dropping funel, reaction a period of time, then vacuum
Filter, with deionized water and ethanol respectively washing three times, after vacuum drying, grind and produce.
Alkaline earth metal hydroxide is now widely used in that high polymer material, wood plastic composite be flame-retardant modified, increasing of timber
Catalysis of tough enhancing and organic synthesis etc..By alkaline earth metal hydroxide nanosizing, its dispersiveness in the material is improved
Can, it will help improve fire-retardant and toughening effect, reduce catalyst amount.Nano alkaline-earth metal hydroxide and paraformaldehyde are answered
With being used for solidifying resorcinol phenol formaldehyde resin adhesive and having no relevant report as curing agent.
The invention has the advantages that by the compounded technology of curing agent, replaced using nano alkaline-earth metal hydroxide
Part paraformaldehyde or other contain curing agent component, prepare new curing agent, meeting《Laminated structure technical specification》State
On the premise of family's standard, free formaldehyde release is reduced, while realize cold curing and high wet strength.
Embodiment
Embodiment 1
By resorcinol phenol formaldehyde resin 100g（Preparation technology is resorcinol：Phenol=1:5, formaldehyde：Phenol=
1.5：1；65-90 DEG C of pre-reaction temperature；65 DEG C of coreaction temperature, coreaction time 2h）, add curing agent（Average grain diameter is
120nm magnesium hydroxide：Paraformaldehyde=1:2）15g and filler（For starch, similarly hereinafter）4g prepares adhesive, is applied in deal board
30 DEG C of cure under pressure 24h after glue, by GB/T 50708-2012 standard testings, dry strength is 14.5MPa (wood-breaking rate 100%), wet
Shear strength is 9.5MPa, and it is 11.9MPa to boil rear shear strength.Laminated wood free formaldehyde is determined by GB/T 14074-2006
Burst size 3.25mg/L.
Embodiment 2
By resorcinol phenol formaldehyde resin 100g（Preparation technology is the same as embodiment 1）, add curing agent（Average grain diameter is
120nm magnesium hydroxides：Paraformaldehyde=2:1）15g and filler 4g, 30 DEG C of cure under pressure 24h after deal board applying glue, by GB/T
50708-2012 standard testings, dry strength are 11.6MPa (wood-breaking rate 100%), and wet shear strength is 6.7MPa, is sheared after boiling
Intensity is 8.0MPa.By GB/T 14074-2006 measure laminated wood free formaldehyde releases 2.15mg/L.
Embodiment 3
By resorcinol phenol formaldehyde resin 100g（Preparation technology is the same as embodiment 1）, add curing agent（Average grain diameter is
150nm calcium hydroxide：Hexamethylenetetramine=2:1）15g and filler 4g, 30 DEG C of cure under pressure 24h after deal board applying glue,
By GB/T 50708-2012 standard testings, dry strength is 12.5MPa (wood-breaking rate 100%), and wet shear strength is 8.1MPa, is boiled
Shear strength is 8.5MPa after boiling.By GB/T 14074-2006 measure laminated wood free formaldehyde releases 2.05mg/L.
Embodiment 4
By resorcinol phenol formaldehyde resin 100g（Preparation technology is the same as embodiment 1）, add curing agent（Average grain diameter is
120nm magnesium hydroxide：Paraformaldehyde：Hexamethylenetetramine=2:2:1）15g and filler 4g, 30 DEG C after deal board applying glue
Cure under pressure 24h, by GB/T 50708-2012 standard testings, dry strength is 13.6MPa (wood-breaking rate 100%), wet shear strength
For 8.7MPa, it is 8.9MPa to boil rear shear strength.Laminated wood free formaldehyde release is determined by GB/T 14074-2006
3.54mg/L。
Comparative example 1
By resorcinol phenol formaldehyde resin 100g（Preparation technology is the same as embodiment 1）, add curing agent（Paraformaldehyde）
15g and filler 4g, 30 DEG C of cure under pressure 24h after deal board applying glue, by GB/T 50708-2012 standard testings, dry strength
For 13.6MPa (wood-breaking rate 100%), wet shear strength is 10.0MPa, and it is 9.7MPa to boil rear shear strength.By GB/T
14074-2006 measure laminated wood free formaldehyde releases 5.65mg/L.
Comparative example 2
By resorcinol phenol formaldehyde resin 100g（Preparation technology is the same as embodiment 1）, add curing agent（Six methines four
Amine：Paraformaldehyde=2:1）15g and filler 4g, 30 DEG C of cure under pressure 24h after deal board applying glue, by GB/T 50708-2012
Standard testing, dry strength are 7.4MPa (wood-breaking rate 80%), and wet shear strength is 1.3MPa, and it is 2.1MPa to boil rear shear strength.
By GB/T 14074-2006 measure laminated wood free formaldehyde releases 3.57mg/L.
By the results showed that of embodiment and comparative example by nano alkaline-earth metal hydroxide and paraformaldehyde and/or
Curative systems prepared by hexamethylenetetramine compounding are glued to structure than single paraformaldehyde or with the curing agent of other compoundings
Wooden glue performance is more preferable.Embodiment 1-4 and the gained veneered product of comparative example 1 can meet that structure gluing wood glue closes the country of intensity
Standard GB/T 50708-2012（（Dry shear strength >=10MPa, wet shear strength >=6MPa, boil rear shear strength >=
6MPa）.Particularly embodiment 1 is significantly larger than national standard.But the free formaldehyde release of comparative example 1 is high（5.65mg/
L）, embodiment 1-4 free formaldehyde release is compared with comparative example 1 to be substantially reduced.The wet shear strength of comparative example 2 and boil
Shear strength is all significantly less than 6MPa national standard after boiling, it is impossible to meets the requirement of structure laminated wood.Illustrate nanometer alkali
Earth metal hydroxide is that one kind can effectively replace part paraformaldehyde（Or its analog）Curing agent component.
Claims (6)
1. a kind of curing agent of laminated wood adhesive, it is characterised in that the component of the curing agent includes nano alkaline-earth metal
Hydroxide and paraformaldehyde, the average grain diameter of the nano alkaline-earth metal hydroxide is no more than 300nm；The nanometer alkali
Earth metal hydroxide accounts for the 20-80wt% of curing agent；The content of the paraformaldehyde is 30-70wt%, the curing agent each group
The dosage sum divided is 100wt%；The curing agent is used to solidify resorcinol phenol formaldehyde resin.
2. curing agent as claimed in claim 1, it is characterised in that the curing agent is 1 by mass ratio:2 nanometer alkaline earth gold
Belong to hydroxide and paraformaldehyde composition.
3. curing agent as claimed in claim 1, it is characterised in that the component of the curing agent includes hexamethylenetetramine.
4. curing agent as claimed in claim 3, it is characterised in that the content of hexamethylenetetramine is 10- in the curing agent
40wt%。
5. curing agent as claimed in claim 1, it is characterised in that the average grain diameter of the nano alkaline-earth metal hydroxide is
60-200nm。
6. curing agent as claimed in claim 1, it is characterised in that the nano alkaline-earth metal hydroxide is nanometer hydroxide
Magnesium and/or nano calcium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510857056.3A CN105440971B (en) | 2015-11-30 | 2015-11-30 | A kind of curing agent of laminated wood adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510857056.3A CN105440971B (en) | 2015-11-30 | 2015-11-30 | A kind of curing agent of laminated wood adhesive |
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| Publication Number | Publication Date |
|---|---|
| CN105440971A CN105440971A (en) | 2016-03-30 |
| CN105440971B true CN105440971B (en) | 2017-12-05 |
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ID=55551629
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4594384A (en) * | 1984-12-21 | 1986-06-10 | Valtion Teknillinen Tutkimuskeskus | Adhesive composition particularly for manufacturing wood constructions, panels and other similar wood products |
| US9163169B2 (en) * | 2012-03-13 | 2015-10-20 | Georgia-Pacific Chemicals Llc | Adhesive compositions having a reduced cure time and methods for making and using same |
| CN103881632B (en) * | 2014-03-21 | 2015-06-17 | 南京林业大学 | Composite curing agent and preparation method thereof |
| CN103865018B (en) * | 2014-04-09 | 2016-01-27 | 中南林业科技大学 | A kind of matrix resin and a kind of structure laminated wood stick with glue agent |
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2015
- 2015-11-30 CN CN201510857056.3A patent/CN105440971B/en active Active
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| CN105440971A (en) | 2016-03-30 |
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