CN105131223A - Melamine modified resin adhesive for flax chip shaving boards, and preparation method thereof - Google Patents
Melamine modified resin adhesive for flax chip shaving boards, and preparation method thereof Download PDFInfo
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- CN105131223A CN105131223A CN201510520591.XA CN201510520591A CN105131223A CN 105131223 A CN105131223 A CN 105131223A CN 201510520591 A CN201510520591 A CN 201510520591A CN 105131223 A CN105131223 A CN 105131223A
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Abstract
The invention discloses a melamine modified resin adhesive for flax chip shaving boards, and a preparation method thereof. The resin adhesive comprises, by weight, 1230-1600 parts of formaldehyde, 1050-1300 parts of melamine, 40-80 parts of diglycol, 30-80 parts of caprolactam and 700-1000 parts of water. Melamine is used to substitute urea in order to be used for synthesizing melamine-formaldehyde resin, so the colorless and semitransparent properties of resin are reserved, and the resin adhesive also has the advantages of suitable storage period, controllable cost, improved water and heat resistance, and solidification at normal temperature.
Description
Technical field
The invention belongs to resin preparation field, particularly a kind of cyanurotriamide modified Resin adhesive for Flaxboard and preparation method.
Background technology
Its thickness of wood raw material for the manufacture of laminated wood is general all at more than 20mm, its length and width are then larger, and timber is the poor conductor of heat, therefore bond the ability of solidifying under large size wood raw material tackiness agent used should possess normal temperature (18 ~ 30 DEG C) condition, or thermatron is set in wood bonding workshop section, to improve the chemical reaction velocity of the tackiness agent of hot conditions solidification in envrionment temperature, quickening.But consider the reasons such as high-frequency heating apparatus investment, equipment operation stability, current domestic laminated wood manufactory tackiness agent used is normal temperature cured type tackiness agent.
The quick-setting wood structure tackiness agent of the normal temperature that present domestic market uses has the large class of resorcinol phenol formaldehyde resin, resorcinol-formaldehyde resin, urea-formaldehyde resin, melamine formaldehyde resin, melamine-urea-formaldehyde resin and urethane five, but has following deficiency:
(1) above-mentioned five large class normal temperature cured type wood adhesive major parts rely on the external import such as Japan, Finland, so far, do not use China to research and develop voluntarily and the ambient cure sqtructural adhesive produced in domestic timber engineering on a large scale, this has potential safety hazard to the Sustainable Healthy Development of the wooden structures component of China;
(2) when glue laminated wood member bonding adopts resorcinol phenol formaldehyde resin and resorcinol-formaldehyde resin, its adhesive property is excellent, but glue-line reddish black, extremely inharmonious in appearance with the pastel shade timber of bondd routine, and the free phenol material contained all has detrimentally affect to the health of people and environment;
(3) glue laminated wood member of urea-formaldehyde resin bonding, use the requirement of conformance with standard specification in the dry state, and resin price is low, but in outdoor or that ambient temperature and humidity change is comparatively violent indoor environment, resin affects greatly by changing environment, molecular chain easy fracture, cohesive strength is lost very fast, and Application Areas is by larger restriction;
(4) melamine formaldehyde resin activity is high, and storage period is short, and the glue-line fragility after solidification is large, and toughness is not enough, and price is higher;
(5) the laminated wood normal temperature cured type melamine-urea-formaldehyde resin temporary unavailability in market at home;
(6) polyurethane based resin price is generally the 2-4 of resorcinol phenol formaldehyde resin doubly, brings difficulty to the cost control of domestic glue laminated wood member manufacturing enterprise.
Urea functionality is 4,4 reactive hydrogen atoms that can be substituted are had in molecule, and trimeric cyanamide functionality is 6, amino whole 6 hydrogen atoms can be replaced by other active substance, have higher reactive behavior, therefore, urea and trimeric cyanamide can with formaldehyde generation chemical reaction, in reaction process, first generate methylol material by addition reaction, reacted by Step Condensation again, formed and there is insoluble not molten build thermosetting resin.
Urea-formaldehyde resin water white transparency or be milky turbidity viscous liquid, generally there is the dry matter content of more than 50%, material cost is lower, but its urea raw material also can dissolve in cold water, resin after solidification is remaining has hydrophilic methylol, glued membrane still has water-absorbent to a certain degree, vulnerable to boiling water, glued membrane is easy to aging, especially at hot and humid environment, therefore urea-formaldehyde resin only can be used for weather condition and fluctuates in little indoor environment, urea reaction activity is lower simultaneously, completion of cure required time is longer at normal temperatures for its resin prepolymer liquid, resin storage period is long.Comparatively speaking, the solubleness of trimeric cyanamide in water is very low, there is again more functionality, therefore can react rapidly with formaldehyde and form more being cross-linked, and trimeric cyanamide itself is ring texture, therefore melamine resin has hardness, the intensity of good water tolerance, thermotolerance and Geng Gao, melamine formaldehyde resin is also water white transparency or is milky turbidity viscous liquid, visual appearance after bonding timber is good, but it is high to there is trimeric cyanamide cost, after resin solidification, property is crisp easy to crack, the deficiency that the active storage period of resin properties is short.
Along with developing rapidly of Chinese society doctrine economic construction, the demand of all trades and professions to timber increases day by day; And China's timber reserves reduces day by day, imbalance between supply and demand is given prominence to, the processing of Wood products can not meet the growing needs of economic production far away, therefore, explore the utilization of non-wooden material---particularly utilize a large amount of annual crop bar to make sheet material to replace wood-base fibre and particle panel material, be more and more subject to people's attention.In recent years, external making sheet is produced to be increased year by year, and Flaxboard substitutes wood-base fibre and particle panel material and obtains applying more and more widely at building field.But the combination of Flaxboard and cyanurotriamide modified Resin adhesive requires high, not only affect the surface quality of glued board, and the bonding strength of glued board can be caused to decline, cause be full of cracks and bubbling.
Summary of the invention
The object of the invention is for solving above-mentioned the deficiencies in the prior art, by being raw material by trimeric cyanamide and methyl alcohol, with production of melamine-formaldehyde resin, not only remain the character of resin semi-transparent clear, also make the advantages such as its storage period is suitable for, controlled, the water-fast thermotolerance of cost improves, normal temperature solidified.
In order to improve the performance of cyanurotriamide modified formaldehyde resin further, the present invention also adopts glycol ether and hexanolactam as properties-correcting agent, improve the temperature applicable range of terpolycyantoamino-formaldehyde resin, result shows, and modified terpolycyantoamino-formaldehyde resin has change in various degree in viscosity, pH value, muddy time, set time.
For achieving the above object, the present invention adopts following technical proposals:
For a cyanurotriamide modified Resin adhesive for Flaxboard, each composition weight number is as follows: formaldehyde 1230-1600 part, trimeric cyanamide 1050-1300 part, glycol ether 40-80 part, hexanolactam 30-80 part, water 700-1000 part.
The effect of glycol ether carries out etherification reaction, enclosure portion methylol with formaldehyde, reduces reactive behavior, strengthens resin stability, improves its hydrophobicity and high temperature resistant, improve its tack.
Wherein, when glycol ether add-on is lower than 40 weight part, hydrophobicity, high thermal resistance are bad, and the initial viscosity of resin is low.On the other hand, if the add-on of glycol ether is higher than 80 weight parts, then cost can be caused to raise.The present invention confirms following result: if during the scope of the content of glycol ether more than 40 weight parts and below 80 weight parts, can obtain the hydrophobicity of expectation, high thermal resistance and initial viscosity.
The effect of caprolactam is modified melamine-formaldehyde resin, encloses the water suction group of resin, and the water tolerance of resin and ageing resistance are significantly improved, and improves muddy time and set time, improves anti-pollution and crack resistance energy.
When the content of caprolactam is lower than 30 weight part, modified resin water tolerance and ageing-resistant decreased effectiveness can be caused, the closing force between the copolymer particle of modified resin declines, and anti-pollution and crack resistance can be bad.
On the other hand, when the content of caprolactam is higher than 80 weight part, high thermal resistance and initial viscosity may be caused to decline, therefore, in the application, the add-on of caprolactam is limited to below 80 weight parts, therefore can not produces the problems referred to above.
Preferably, each composition weight number is as follows: formaldehyde 1230-1500 part, trimeric cyanamide 1050-1100 part, glycol ether 40-50 part, hexanolactam 30-60 part, water 700-800 part.
Preferably, each composition weight number is as follows: 1230 parts, formaldehyde, trimeric cyanamide 1050 parts, glycol ether 40 parts, hexanolactam 30 parts, 700 parts, water.
Present invention also offers a kind of preparation method of the cyanurotriamide modified Resin adhesive for Flaxboard, mixed with water by formaldehyde, adjustment pH value is 8.5-9.5, adds trimeric cyanamide and glycol ether successively, heat up, be incubated at 85 DEG C-87 DEG C, survey between PH8.3-9.0, in 10 degree of water, survey cloud point, after going out cloud point, survey water smoke multiple, when water smoke doubly counts to 1:3, cooling; When cooling to 40-42 DEG C, add caprolactam, adjustment PH is 8.5-9.5, and water-soluble multiple is 1:2-4, insulation 15-20 minute; Stop cooling, blowing, to obtain final product.
Above-mentioned cyanurotriamide modified Resin adhesive with decorative encasing shaving board or can prepare laminated structure component.
The present invention is owing to taking above technical scheme, and it has the following advantages:
The present invention is on traditional melamine formaldehyde resin synthesis technique basis, determine in initial reaction stage, directly polycondensation is carried out with trimeric cyanamide and formaldehyde, when reaction solution Free-formaldehyde content is less, add the larger glycol ether of reactive behavior again, in the later stage in the reaction, strictly control reacting liquid pH value, building-up process controlledly can be carried out, finally add caprolactam again and carry out further modification.Reaction process is steadily easy to control, favorable repeatability.
2. prepare laminated structure component with the melamine formaldehyde resin of synthesis, it adhesive property comprising bonding strength, wood-breaking rate and glue-line integrity can meet the middle II class tackiness agent of " structural glulam " (GB26899-2011) with " timber structure test method standard " (GB/T50329-2002) to the requirement of tackiness agent.Resin normal temperature condition can realize solidification, and workable, cohesive strength is high, can meet the actual needs of structural glulam.
3. the shelf lives of resin of the present invention is greater than 7 days, and color of resin is milky white to translucent, and the timber glue-line color coordination that bonding look shallow is good, and Application Areas is wide.
4. take full advantage of the high reaction activity of glycol ether and hexanolactam, and the low cost of melamine formaldehyde resin and toughness, invention cyanurotriamide modified resin owing to not adding urea, avoid urea raw material to dissolve in cold water, the remaining problem with hydrophilic methylol of resin after solidification, glued membrane infiltration is strong, and strong to boiling water resistibility, glued membrane is not easy to aging.
5, the present invention is simple to operate, practical, is easy to promote.
Embodiment
Mode by the following examples further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, conventionally selects with condition.
Embodiment 1:
For a cyanurotriamide modified Resin adhesive for Flaxboard, each composition weight number is as follows: 12300 parts, formaldehyde, trimeric cyanamide 1050 parts, glycol ether 40 parts, hexanolactam 30 parts, 700 parts, water.
Preparation method is as follows: mixed with water by formaldehyde, regulates pH value to be about 9.0, adds trimeric cyanamide and glycol ether successively, heats up, be incubated at 85 DEG C-87 DEG C, survey between PH8.3-9.0, in 10 degree of water, survey cloud point, after going out cloud point, survey water smoke multiple, when water smoke doubly counts to 1:3, cooling; When cooling to 40 DEG C, add caprolactam, regulate about PH9.0, water-soluble multiple is 1:2, is incubated 15 minutes; Stop cooling, blowing, to obtain final product.
The resin technology index of embodiment 1 is as follows:
Table 1
| Outward appearance | Water white transparency, inclusion-free |
| Solids content (%) | 60-65 |
| Viscosity S/20 DEG C | 25-30 is coated with 4# cup |
| Free methanol (%) | ≦0.2 |
| PH value | 7.0-7.5 |
| Storage period | 7-10 days |
The detection of cyanurotriamide modified Resin adhesive in subordinate list 1, solids content detects by 3.5 regulations of GB/T14074-2006, viscosity detects by 3.3 regulations of GB/T14074-2006, set time is detected by 3.7 regulations of GB/T14074-2006, free formaldehyde detects by 3.16 regulations of GB/T14074-2006, the unified solids content referring to institute's glue of solids content, the massfraction of free formaldehyde content unreacted monomer formaldehyde contained by the inside of whole glue.
The urea-formaldehyde-modified Resin adhesive pressing plate of E1/E0 level type Ⅰ plywood embodiment 1 detects
The glued board room temperature of compacting is placed after 5 ~ 7 days and is detected.Bonding strength by GB/T17657-1999 4.15 regulation detect, burst size of methanal detects by 4.12 condensed steam water in GB/T17657-1999.Veneer: shive veneer, heat pressing process: 120-130 DEG C, 1.0Mpa, hot pressing time: 5min.
Result shows:
100 DEG C of boiling water boiling 9h bonding strengths are 1.45Mpa, and qualification rate is 100%, Jia aldehyde Shi Fang Liang≤0.14mg/l.The resistance to be full of cracks in surface: 0 grade, pollution-free corrosion-free.
Embodiment 2:
For a cyanurotriamide modified Resin adhesive for Flaxboard, each composition weight number is as follows: 1600 parts, formaldehyde, trimeric cyanamide 1300 parts, glycol ether 80 parts, hexanolactam 80 parts, 1000 parts, water.
Preparation method is as follows: mixed with water by formaldehyde, regulates pH value to be about 9.0, adds trimeric cyanamide and glycol ether successively, heats up, be incubated at 85 DEG C-87 DEG C, survey between PH8.3-9.0, in 10 degree of water, survey cloud point, after going out cloud point, survey water smoke multiple, when water smoke doubly counts to 1:3, cooling; When cooling to 42 DEG C, add caprolactam, regulate about PH9.0, water-soluble multiple is 1:4, is incubated 20 minutes; Stop cooling, blowing, to obtain final product.
The resin technology index of embodiment 2 is as follows:
Table 2
| Outward appearance | Water white transparency, inclusion-free |
| Solids content (%) | 60-65 |
| Viscosity S/20 DEG C | 25-30 is coated with 4# cup |
| Free methanol (%) | ≦0.2 |
| PH value | 7.0-7.5 |
| Storage period | 7-10 days |
The detection of cyanurotriamide modified Resin adhesive in subordinate list 1, solids content detects by 3.5 regulations of GB/T14074-2006, viscosity detects by 3.3 regulations of GB/T14074-2006, set time is detected by 3.7 regulations of GB/T14074-2006, free formaldehyde detects by 3.16 regulations of GB/T14074-2006, the unified solids content referring to institute's glue of solids content, the massfraction of free formaldehyde content unreacted monomer formaldehyde contained by the inside of whole glue.
The urea-formaldehyde-modified Resin adhesive pressing plate of E1/E0 level type Ⅰ plywood embodiment 1 detects
The glued board room temperature of compacting is placed after 5 ~ 7 days and is detected.Bonding strength by GB/T17657-1999 4.15 regulation detect, burst size of methanal detects by 4.12 condensed steam water in GB/T17657-1999.Veneer: shive veneer, heat pressing process: 120-130 DEG C, 1.0Mpa, hot pressing time: 5min.
Result shows:
100 DEG C of boiling water boiling 9h bonding strengths are 1.43Mpa, and qualification rate is 100%, Jia aldehyde Shi Fang Liang≤0.13mg/l.The resistance to be full of cracks in surface: 0 grade, pollution-free corrosion-free.
Embodiment 3:
For a cyanurotriamide modified Resin adhesive for Flaxboard, each composition weight number is as follows: 1500 parts, formaldehyde, trimeric cyanamide 1100 parts, glycol ether 50 parts, hexanolactam 60 parts, 800 parts, water.
Preferably, each composition weight number is as follows: 1230 parts, formaldehyde, trimeric cyanamide 1050 parts, glycol ether 40 parts, hexanolactam 30 parts, 700 parts, water.
Preparation method is as follows: mixed with water by formaldehyde, regulates pH value to be about 9.0, adds trimeric cyanamide and glycol ether successively, heats up, be incubated at 85 DEG C-87 DEG C, survey between PH8.3-9.0, in 10 degree of water, survey cloud point, after going out cloud point, survey water smoke multiple, when water smoke doubly counts to 1:3, cooling; When cooling to 40 DEG C, add caprolactam, regulate about PH9.0, water-soluble multiple is 1:2, is incubated 15 minutes; Stop cooling, blowing, to obtain final product.
The resin technology index of embodiment 3 is as follows:
Table 3
| Outward appearance | Water white transparency, inclusion-free |
| Solids content (%) | 60-65 |
| Viscosity S/20 DEG C | 25-30 is coated with 4# cup |
| Free methanol (%) | ≦0.2 |
| PH value | 7.0-7.5 |
| Storage period | 7-10 days |
The detection of cyanurotriamide modified Resin adhesive in subordinate list 1, solids content detects by 3.5 regulations of GB/T14074-2006, viscosity detects by 3.3 regulations of GB/T14074-2006, set time is detected by 3.7 regulations of GB/T14074-2006, free formaldehyde detects by 3.16 regulations of GB/T14074-2006, the unified solids content referring to institute's glue of solids content, the massfraction of free formaldehyde content unreacted monomer formaldehyde contained by the inside of whole glue.
The urea-formaldehyde-modified Resin adhesive pressing plate of E1/E0 level type Ⅰ plywood embodiment 1 detects
The glued board room temperature of compacting is placed after 5 ~ 7 days and is detected.Bonding strength by GB/T17657-1999 4.15 regulation detect, burst size of methanal detects by 4.12 condensed steam water in GB/T17657-1999.Veneer: shive veneer, heat pressing process: 120-130 DEG C, 1.0Mpa, hot pressing time: 5min.
Result shows:
100 DEG C of boiling water boiling 9h bonding strengths are 1.41Mpa, and qualification rate is 100%, Jia aldehyde Shi Fang Liang≤0.12mg/l.The resistance to be full of cracks in surface: 0 grade, pollution-free corrosion-free.
Although above-mentioned, the specific embodiment of the present invention is described; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention; those skilled in the art do not need to pay creative work; the various amendment that can make or distortion, still within protection scope of the present invention.
Claims (7)
1. for a cyanurotriamide modified Resin adhesive for Flaxboard, it is characterized in that, each composition weight number is as follows: formaldehyde 1230-1600 part, trimeric cyanamide 1050-1300 part, glycol ether 40-80 part, hexanolactam 30-80 part, water 700-1000 part.
2. cyanurotriamide modified Resin adhesive as claimed in claim 1, is characterized in that, each composition weight number is as follows: formaldehyde 1230-1500 part, trimeric cyanamide 1050-1100 part, glycol ether 40-50 part, hexanolactam 30-60 part, water 700-800 part.
3. cyanurotriamide modified Resin adhesive as claimed in claim 1, is characterized in that, each composition weight number is as follows: 1230 parts, formaldehyde, trimeric cyanamide 1050 parts, glycol ether 40 parts, hexanolactam 30 parts, 700 parts, water.
4., for a preparation method for the cyanurotriamide modified Resin adhesive of Flaxboard, it is characterized in that, formaldehyde is mixed with water, adjustment pH value is 8.5-9.5, add trimeric cyanamide and glycol ether successively, heat up, be incubated at 85 DEG C-87 DEG C, survey between PH8.3-9.0, in 10 degree of water, survey cloud point, after going out cloud point, survey water smoke multiple, when water smoke doubly counts to 1:3, cooling; When cooling to 40-42 DEG C, add caprolactam, adjustment PH is 8.5-9.5, and water-soluble multiple is 1:2-4, insulation 15-20 minute; Stop cooling, blowing, to obtain final product.
5. the cyanurotriamide modified Resin adhesive prepared of method according to claim 4.
6. claim 1-3,5 application of arbitrary described cyanurotriamide modified Resin adhesive in facing shaving board decoration.
7. claim 1-3,5 arbitrary described cyanurotriamide modified Resin adhesives are preparing the application in laminated structure component.
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| CN105524582A (en) * | 2015-12-31 | 2016-04-27 | 广东福美新材料科技有限公司 | Melamine adhesive and preparing method thereof |
| CN107526198A (en) * | 2017-08-23 | 2017-12-29 | 京东方科技集团股份有限公司 | A kind of display device |
| CN108034031A (en) * | 2017-12-11 | 2018-05-15 | 云南新泽兴人造板有限公司 | A kind of high-concentration formaldehyde Lauxite preshrunk liquid synthesis technique |
| CN109880034A (en) * | 2019-01-25 | 2019-06-14 | 广东天元汇邦新材料股份有限公司 | A kind of melamine resin and its preparation method and application of anti-finger-marks |
| CN110894273A (en) * | 2019-12-05 | 2020-03-20 | 江苏长顺高分子材料研究院有限公司 | Melamine aldehyde-based adhesive resin with good storage stability and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105524582A (en) * | 2015-12-31 | 2016-04-27 | 广东福美新材料科技有限公司 | Melamine adhesive and preparing method thereof |
| CN107526198A (en) * | 2017-08-23 | 2017-12-29 | 京东方科技集团股份有限公司 | A kind of display device |
| CN107526198B (en) * | 2017-08-23 | 2020-07-28 | 京东方科技集团股份有限公司 | Display device |
| CN108034031A (en) * | 2017-12-11 | 2018-05-15 | 云南新泽兴人造板有限公司 | A kind of high-concentration formaldehyde Lauxite preshrunk liquid synthesis technique |
| CN109880034A (en) * | 2019-01-25 | 2019-06-14 | 广东天元汇邦新材料股份有限公司 | A kind of melamine resin and its preparation method and application of anti-finger-marks |
| CN109880034B (en) * | 2019-01-25 | 2021-09-28 | 广东天元汇邦新材料股份有限公司 | Anti-fingerprint melamine resin and preparation method and application thereof |
| CN110894273A (en) * | 2019-12-05 | 2020-03-20 | 江苏长顺高分子材料研究院有限公司 | Melamine aldehyde-based adhesive resin with good storage stability and preparation method thereof |
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