CN102604575A - Modified urea formaldehyde adhesive and preparation method thereof - Google Patents
Modified urea formaldehyde adhesive and preparation method thereof Download PDFInfo
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- CN102604575A CN102604575A CN201210092963XA CN201210092963A CN102604575A CN 102604575 A CN102604575 A CN 102604575A CN 201210092963X A CN201210092963X A CN 201210092963XA CN 201210092963 A CN201210092963 A CN 201210092963A CN 102604575 A CN102604575 A CN 102604575A
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Abstract
The invention discloses and relates to a modified urea formaldehyde adhesive and a preparation method of the modified urea formaldehyde adhesive. The modified urea formaldehyde adhesive disclosed by the invention solves the problems of poor stability and short storage time of the urea formaldehyde adhesive in prior arts. The urea formaldehyde adhesive disclosed by the invention comprises formaldehyde, urea, melamine, phenol, sodium cellulose, ammonia water, and polyvinyl alcohol. The preparation method comprises the following steps: (1) weighing each component, heating to 30-35 DEG C, regulating pH value, and adding sodium cellulose; (2) heating, adding the first part of urea, and regulating the pH value; (3) increasing the temperature to 92 DEG C, regulating the pH value, and holding temperature for reaction; and (4) regulating the pH value, observing the reaction end-point, regulating the pH value to finish the reaction, adding the second part of urea, mixing, decreasing the temperature to 70 DEG C, adding the third part of urea and the residual components, decreasing the temperature, regulating the pH value, and discharging to obtain the modified urea formaldehyde adhesive. The free formaldehyde content in the urea formaldehyde adhesive provided by the invention is less than 0.1%, and the storage time is two months. The modified urea formaldehyde adhesive provided by the invention is applied to the field of urea-formaldehyde adhesive.
Description
Technical field
The present invention relates to a kind of modified urea-formaldehyde glue and preparation method thereof.
Background technology
At present, be applied to the urea-formaldehyde glue of wood-processing industry, main raw material is formaldehyde and urea.Wherein formaldehyde content is very high, and formaldehyde has the characteristics of high volatility, and evaporable gas is stronger to people's pungency, and is harmful to health of human body.Become current urgent problem so study hypotoxic urea-formaldehyde glue.Come in, novel modified urea-formaldehyde glue is adopted in existing relevant report research, can make free formaldehyde content be lower than 0.5%; But, there be the stable low of glue again, storage time is short, does not have precompressed in the course of processing; Make the wood veneer quality low, thereby increase labour intensity, be unfavorable for the raising of working efficiency, and existing urea-formaldehyde glue is in the impregnation process; Exist solidified dangerous, be lower than 4.6, just have the solidified phenomenon such as pH when the impregnation.
Summary of the invention
The objective of the invention is to have the urea-formaldehyde glue poor stability now in order to solve, the problem that the storage time is short, and a kind of modified urea-formaldehyde glue and preparation method thereof is provided.
A kind of modified urea-formaldehyde glue of the present invention is to be that 37% formaldehyde, 300~400 parts urea, 35~45 parts trimeric cyanamide, 3~7 parts phenol, 3~7 parts sodium cellulosate, 3~7 parts quality percentage composition are that 25%~28% ammoniacal liquor and 3~7 parts Z 150PH are processed by 600~700 parts quality percentage composition by ratio of weight and the number of copies.
The preparation method of a kind of modified urea-formaldehyde glue of the present invention carries out according to following steps:
One, taking by weighing 600~700 parts quality percentage composition by ratio of weight and the number of copies is that 37% formaldehyde, 35~45 parts trimeric cyanamide, 3~7 parts phenol, 3~7 parts sodium cellulosate, 3~7 parts quality percentage composition are 25%~28% ammoniacal liquor and 3~7 parts Z 150PH;
Two, the quality percentage composition that step 1 is taken by weighing is that 37% formaldehyde adds in the reaction kettle; Heat temperature raising; When the pressure of boiler reaches 0.3MPa; When the formaldehyde temperature in the reaction kettle reached 30 ℃~35 ℃, use concentration was caustic soda solution adjusting formaldehyde pH to 7.5~8.0 of 25%~30%, adds the sodium cellulosate that step 1 takes by weighing again;
When three, continuing to be heated to formaldehyde temperature in the reaction kettle and reach 36 ℃~40 ℃; Use concentration is 25%~30% caustic soda solution adjusting formaldehyde pH to 8.0; The urea that adds 200~220 weight parts; Mix, get and just mix liquid, employing concentration is the first liquid pH to 6.3 of mixing of caustic soda solution adjusting~6.5 of 25%~30%;
Four, continuing reacting by heating still to temperature is 72 ℃~78 ℃; BP stops heating when being 1.5~2.0MPa; Lean on reaction kettle self heat release to be warming up to 92 ℃; Adopting concentration again is pH value of solution to 6.3~6.5 of solution in 25%~30% the caustic soda solution conditioned reaction still, insulation reaction 30~40 minutes, mixed solution;
Five, adopting concentration is pH of mixed to 4.8~5.0 that 25%~28% ammonium chloride solution regulating step four obtains, and mixed solution is added drop-wise to when observing to reaction end in 8~10 ℃ of water, and using concentration again is that 25%~30% caustic soda solution is regulated pH of mixed to 6.7~7.2; The urea that adds 90~100 weight parts again mixed 10~20 minutes, and mixed solution is cooled to 70 ℃; Add the urea of 10~20 weight parts, phenol, ammoniacal liquor and the trimeric cyanamide that step 1 takes by weighing then; After stirring, when mixed solution was cooled to 40 ℃, using concentration again was that 25%~30% caustic soda solution is regulated pH of mixed value to 7.5~8.5; Put glue, promptly get urea-formaldehyde glue; Described reaction reach terminal point be meant with being coated with-4 glasss record viscosity and reach 25~30 seconds/25 ℃.
Beneficial effect of the present invention:
The ammoniacal liquor that adds in the urea-formaldehyde glue of the present invention can further reduce formaldehyde content, and the phenol of adding can make glue can further increase the hot water property of glue, makes content of free aldehyde reduce to very low value, and urea-formaldehyde glue free formaldehyde content of the present invention is lower than 0.1%.
Sodium cellulosate in the urea-formaldehyde glue of the present invention can improve the tack of glue, improves the water-soluble of glue, and urea-formaldehyde glue can be reacted in 8 ℃~10 ℃ environment, improves urea-formaldehyde glue stability; And can make glue store 2 months, more existing urea-formaldehyde glue storage was compared and is significantly improved in 1 month.Urea-formaldehyde glue of the present invention adds Z 150PH in the actual course of processing, make the precompressed property raising of wood veneer; Compare the wood veneer of present no precompressed, can improve the quality of wood veneer, owing to carry out precompressed in advance; Therefore; Can save working efficiency, have problems such as skew when avoiding, influence working efficiency because of the compacting wood veneer.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: a kind of modified urea-formaldehyde glue of this embodiment is to be that 37% formaldehyde, 300~400 parts urea, 35~45 parts trimeric cyanamide, 3~7 parts phenol, 3~7 parts sodium cellulosate, 3~7 parts quality percentage composition are that 25%~28% ammoniacal liquor and 3~7 parts Z 150PH are processed by 600~700 parts quality percentage composition by ratio of weight and the number of copies.
The ammoniacal liquor that adds in the urea-formaldehyde glue of this embodiment can further reduce formaldehyde content; The phenol that adds can make glue can further increase the hot water property of glue; Make content of free aldehyde reduce to very low value, this embodiment urea-formaldehyde glue free formaldehyde content is lower than 0.1%.
Sodium cellulosate in the urea-formaldehyde glue of this embodiment can improve the tack of glue, improves the water-soluble of glue, and urea-formaldehyde glue can be reacted in 8 ℃~10 ℃ environment, improves urea-formaldehyde glue stability; And can make glue store 2 months, more existing urea-formaldehyde glue storage was compared and is significantly improved in 1 month.The urea-formaldehyde glue of this embodiment adds Z 150PH in the actual course of processing, make the precompressed property raising of wood veneer; Compare the wood veneer of present no precompressed, can improve the quality of wood veneer, owing to carry out precompressed in advance; Therefore; Can save working efficiency, have problems such as skew when avoiding, influence working efficiency because of the compacting wood veneer.
Embodiment two: what this embodiment and embodiment one were different is: urea-formaldehyde glue is that 37% formaldehyde, 333 parts urea, 40 parts trimeric cyanamide, 5 parts phenol, 5 parts sodium cellulosate, 5 parts quality percentage composition are that 25%~28% ammoniacal liquor and 5 parts Z 150PH are formed by 666 parts quality percentage composition by weight.Other is identical with embodiment one.
Embodiment three: the preparation method of a kind of modified urea-formaldehyde glue of this embodiment carries out according to following steps: the quality percentage composition that, takes by weighing 600~700 parts by ratio of weight and the number of copies is that 37% formaldehyde, 35~45 parts trimeric cyanamide, 3~7 parts phenol, 3~7 parts sodium cellulosate, 3~7 parts quality percentage composition are 25%~28% ammoniacal liquor and 3~7 parts Z 150PH;
Two, the quality percentage composition that step 1 is taken by weighing is that 37% formaldehyde adds in the reaction kettle; Through the boiler heat temperature raising; When the pressure of boiler reaches 0.3 MPa; When the formaldehyde temperature in the reaction kettle reached 30 ℃~35 ℃, use concentration was caustic soda solution adjusting formaldehyde pH to 7.5~8.0 of 25%~30%, adds the sodium cellulosate that step 1 takes by weighing again;
When three, continuing to be heated to formaldehyde temperature in the reaction kettle and reach 36 ℃~40 ℃; Use concentration is 25%~30% caustic soda solution adjusting formaldehyde pH to 8.0; The urea that adds 200~220 weight parts; Mix, get and just mix liquid, employing concentration is the first liquid pH to 6.3 of mixing of caustic soda solution adjusting~6.5 of 25%~30%;
Four, continuing reacting by heating still to temperature is 72 ℃~78 ℃; BP stops heating when being 1.5~2.0MPa; Lean on reaction kettle self heat release to be warming up to 92 ℃; Adopting concentration again is pH value of solution to 6.3~6.5 of solution in 25%~30% the caustic soda solution conditioned reaction still, insulation reaction 30~40 minutes, mixed solution;
Five, adopting concentration is pH of mixed to 4.8~5.0 that 25%~28% ammonium chloride solution regulating step four obtains, and mixed solution is added drop-wise to when observing to reaction end in 8~10 ℃ of water, and using concentration again is that 25%~30% caustic soda solution is regulated pH of mixed to 6.7~7.2; The urea that adds 90~100 weight parts again mixed 10~20 minutes, and mixed solution is cooled to 70 ℃; Add the urea of 10~20 weight parts, phenol, ammoniacal liquor and the trimeric cyanamide that step 1 takes by weighing then; After stirring, when mixed solution was cooled to 40 ℃, using concentration again was that 25%~30% caustic soda solution is regulated pH of mixed value to 7.5~8.5; Put glue, promptly get urea-formaldehyde glue; Described reaction reach terminal point be meant with being coated with-4 glasss record viscosity and reach 25~30 seconds/25 ℃.
The ammoniacal liquor that adds in the urea-formaldehyde glue of this embodiment can further reduce formaldehyde content; The phenol that adds can make glue can further increase the hot water property of glue; Make content of free aldehyde reduce to very low value, this embodiment urea-formaldehyde glue free formaldehyde content is lower than 0.1%.
Sodium cellulosate in the urea-formaldehyde glue of this embodiment can improve the tack of glue, improves the water-soluble of glue, and urea-formaldehyde glue can be reacted in 8 ℃~10 ℃ environment, improves urea-formaldehyde glue stability; And can make glue store 2 months, more existing urea-formaldehyde glue storage was compared and is significantly improved in 1 month.The urea-formaldehyde glue of this embodiment adds Z 150PH in the actual course of processing, make the precompressed property raising of wood veneer; Compare the wood veneer of present no precompressed, can improve the quality of wood veneer, owing to carry out precompressed in advance; Therefore; Can save working efficiency, have problems such as skew when avoiding, influence working efficiency because of the compacting wood veneer.
Specifically be embodiment four: what this embodiment and embodiment three were different is: the formaldehyde temperature in the described reaction kettle of step 2 is 32 ℃~34 ℃.Other step and parameter are identical with step 3.
Specifically be embodiment five: what this embodiment and embodiment three to four were different is: the described quality percentage composition that takes by weighing 666 parts by ratio of weight and the number of copies of step 1 is that 37% formaldehyde, 333 parts urea, 40 parts trimeric cyanamide, 5 parts phenol, 5 parts sodium cellulosate, 5 parts quality percentage composition are 25%~28% ammoniacal liquor and 5 parts Z 150PH.Other step and parameter are identical with step 3 to four.
Specifically be embodiment six: what this embodiment was different with one of embodiment three to five is: the described pH of step 2 is 7.8.Other step and parameter are identical with one of step 3 to five.
Specifically be embodiment seven: what this embodiment was different with one of embodiment three to six is: the described reacting by heating still of step 4 to temperature is 74 ℃~76 ℃.Other step and parameter are identical with one of step 3 to six.
Specifically be embodiment eight: what this embodiment was different with one of embodiment three to seven is: the described insulation reaction of step 4 35 minutes.Other step and parameter are identical with one of step 3 to seven.
Specifically be embodiment nine: what this embodiment was different with one of embodiment three to eight is: step 5 is described to be added drop-wise to mixed solution when observing to reaction end in 8~10 ℃ of water, and using concentration again is that 25%~30% caustic soda solution is regulated pH of mixed to 7.0.Other step and parameter are identical with one of step 3 to eight.
Specifically be embodiment ten: what this embodiment was different with one of embodiment three to eight is: step 5 is described when mixed solution is cooled to 40 ℃, and using concentration again is that 25%~30% caustic soda solution is regulated pH of mixed value to 7.8~82.Other step and parameter are identical with one of step 3 to eight.
Through following verification experimental verification effect of the present invention:
Test
The preparation method of a kind of modified urea-formaldehyde glue of this test carries out according to following steps:
One, takes by weighing the formaldehyde of the concentration 37% of 666kg, the trimeric cyanamide of 40kg, the phenol of 5kg, the sodium cellulosate of 5kg and the Z 150PH of 5kg by ratio of weight and the number of copies;
Two, the concentration that step 1 is taken by weighing is that 37% formaldehyde adds in the reaction kettle, heat temperature raising, and when reaction kettle pressure reaches 0.3Mpa, when temperature was 35 ℃, using concentration was that 25% caustic soda solution is regulated formaldehyde pH to 8.0, adds the sodium cellulosate that step 1 takes by weighing again;
Three, continue reacting by heating still to 40 ℃, using concentration is after 25% caustic soda solution is regulated pH to 8.0, adds the urea of 214kg first, mix, just mix liquid, adopting concentration is that 25% caustic soda solution is regulated and just mixed liquid pH to 6.5;
Four, continuing the reacting by heating still is 75 ℃ to temperature, and pressure stops heating during for 1.8Mpa, leans on self heat release to be warming up to 92 ℃, and adopting concentration is that 25% caustic soda solution is regulated pH to 6.5, insulation reaction 30 minutes, mixed solution;
Five, adopting the quality percentage composition is the pH of mixed to 5.0 that 28% ammonium chloride solution regulating step four obtains, and observes to reach reaction end, records viscosity and reaches 25~30 seconds with being coated with-4 glasss/8 ℃; Using concentration again is that 25% caustic soda solution is regulated pH to 7.2, adds the urea of 99kg again, mixes 15 minutes; Mixed solution is cooled to 70 ℃, adds the urea of 20kg, phenol and the trimeric cyanamide that step 1 takes by weighing then, after stirring; When mixed solution is continued to be cooled to 40 ℃; Use concentration is 25% caustic soda solution adjusting pH of mixed value to 8.0, puts glue, promptly gets urea-formaldehyde glue.
The urea-formaldehyde glue that this test makes can be deposited 2 months, and the urea-formaldehyde glue shelf-time is 2 months, than 1 times of existing increase; The urea-formaldehyde glue free formaldehyde content that this test obtains is lower than 0.1%.The enough environment at 8 ℃~10 ℃ of this test urea-formaldehyde glue react.
Claims (10)
1. modified urea-formaldehyde glue is characterized in that urea-formaldehyde glue is by ratio of weight and the number of copies is that 37% formaldehyde, 300~400 parts urea, 35~45 parts trimeric cyanamide, 3~7 parts phenol, 3~7 parts sodium cellulosate, 3~7 parts quality percentage composition are that 25%~28% ammoniacal liquor and 3~7 parts Z 150PH are processed by 600~700 parts quality percentage composition.
2. a kind of modified urea-formaldehyde glue according to claim 1 is characterized in that urea-formaldehyde glue is that 37% formaldehyde, 333 parts urea, 40 parts trimeric cyanamide, 5 parts phenol, 5 parts sodium cellulosate, 5 parts quality percentage composition are that 25%~28% ammoniacal liquor and 5 parts Z 150PH are formed by 666 parts quality percentage composition by weight.
3. the preparation method of a kind of modified urea-formaldehyde glue as claimed in claim 1 is characterized in that a kind of preparation method of modified urea-formaldehyde glue carries out according to following steps:
One, taking by weighing 600~700 parts quality percentage composition by ratio of weight and the number of copies is that 37% formaldehyde, 35~45 parts trimeric cyanamide, 3~7 parts phenol, 3~7 parts sodium cellulosate, 3~7 parts quality percentage composition are 25%~28% ammoniacal liquor and 3~7 parts Z 150PH;
Two, the quality percentage composition that step 1 is taken by weighing is that 37% formaldehyde adds in the reaction kettle; Through the boiler heat temperature raising; When the pressure of boiler reaches 0.3MPa; When the formaldehyde temperature in the reaction kettle reached 30 ℃~35 ℃, use concentration was caustic soda solution adjusting formaldehyde pH to 7.5~8.0 of 25%~30%, adds the sodium cellulosate that step 1 takes by weighing again;
When three, continuing to be heated to formaldehyde temperature in the reaction kettle and reach 36 ℃~40 ℃; Use concentration is 25%~30% caustic soda solution adjusting formaldehyde pH to 8.0; The urea that adds 200~220 weight parts; Mix, get and just mix liquid, employing concentration is the first liquid pH to 6.3 of mixing of caustic soda solution adjusting~6.5 of 25%~30%;
Four, continuing reacting by heating still to temperature is 72 ℃~78 ℃; BP stops heating when being 1.5~2.0MPa; Lean on reaction kettle self heat release to be warming up to 92 ℃; Adopting concentration again is pH value of solution to 6.3~6.5 of solution in 25%~30% the caustic soda solution conditioned reaction still, insulation reaction 30~40 minutes, mixed solution;
Five, adopting concentration is pH of mixed to 4.8~5.0 that 25%~28% ammonium chloride solution regulating step four obtains, and mixed solution is added drop-wise to when observing to reaction end in 8~10 ℃ of water, and using concentration again is that 25%~30% caustic soda solution is regulated pH of mixed to 6.7~7.2; The urea that adds 90~100 weight parts again mixed 10~20 minutes, and mixed solution is cooled to 70 ℃; Add the urea of 10~20 weight parts, phenol, ammoniacal liquor and the trimeric cyanamide that step 1 takes by weighing then; After stirring, when mixed solution was cooled to 40 ℃, using concentration again was that 25%~30% caustic soda solution is regulated pH of mixed value to 7.5~8.5; Put glue, promptly get urea-formaldehyde glue; Described reaction reach terminal point be meant with being coated with-4 glasss record viscosity and reach 25~30 seconds/25 ℃.
4. the preparation method of a kind of modified urea-formaldehyde glue according to claim 3 is characterized in that the formaldehyde temperature in the described reaction kettle of step 2 is 32 ℃~34 ℃.
5. the preparation method of a kind of modified urea-formaldehyde glue according to claim 3 is characterized in that the described quality percentage composition that takes by weighing 666 parts by ratio of weight and the number of copies of step 1 is that 37% formaldehyde, 333 parts urea, 40 parts trimeric cyanamide, 5 parts phenol, 5 parts sodium cellulosate, 5 parts quality percentage composition are 25%~28% ammoniacal liquor and 5 parts Z 150PH.
6. the preparation method of a kind of modified urea-formaldehyde glue according to claim 3 is characterized in that the described pH of step 2 is 7.8.
7. the preparation method of a kind of modified urea-formaldehyde glue according to claim 3 is characterized in that the described reacting by heating still of step 4 to temperature is 74 ℃~76 ℃.
8. the preparation method of a kind of modified urea-formaldehyde glue according to claim 3 is characterized in that the described insulation reaction of step 4 35 minutes.
9. the preparation method of a kind of modified urea-formaldehyde glue according to claim 3 is characterized in that step 5 is described mixed solution is added drop-wise to when observing to reaction end in 8~10 ℃ of water, and using concentration again is that 25%~30% caustic soda solution is regulated pH of mixed to 7.0.
10. the preparation method of a kind of modified urea-formaldehyde glue according to claim 3, when it is characterized in that step 5 is described mixed solution being cooled to 40 ℃, using concentration again is that 25%~30% caustic soda solution is regulated pH of mixed value to 7.8~8.2.
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Cited By (5)
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CN103540283A (en) * | 2013-10-18 | 2014-01-29 | 巫溪县迪纳木业有限公司 | Urea-formaldehyde glue adhesive and preparation method thereof |
CN103555241A (en) * | 2013-11-22 | 2014-02-05 | 黑龙江大学 | Flame-retardant modified urea-formaldehyde glue and application thereof |
CN103666349A (en) * | 2013-11-22 | 2014-03-26 | 黑龙江大学 | Anti-aging modified urea-formaldehyde glue and preparation method thereof |
CN107118722A (en) * | 2017-05-27 | 2017-09-01 | 柳州市鹏森木业加工有限公司 | A kind of wood-based plate urea-formaldehyde resin adhesive and its preparation technology |
CN108690541A (en) * | 2017-04-10 | 2018-10-23 | 大亚人造板集团有限公司 | A kind of outdoor version fibre board use modified urea-formaldehyde resin adhesive and preparation method thereof |
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CN101265314A (en) * | 2008-04-30 | 2008-09-17 | 北京化工大学 | Environmental protection urea-formaldehyde resin and preparation method thereof |
CN102086295A (en) * | 2010-06-28 | 2011-06-08 | 永港伟方(北京)科技股份有限公司 | Urea-formaldehyde resin for non-dewatering particleboard and preparation method thereof |
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CN1461786A (en) * | 2002-05-31 | 2003-12-17 | 汪正红 | Manufacturing method of environmental protection type urea-formaldehyde resin glue |
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CN103540283A (en) * | 2013-10-18 | 2014-01-29 | 巫溪县迪纳木业有限公司 | Urea-formaldehyde glue adhesive and preparation method thereof |
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CN103666349A (en) * | 2013-11-22 | 2014-03-26 | 黑龙江大学 | Anti-aging modified urea-formaldehyde glue and preparation method thereof |
CN108690541A (en) * | 2017-04-10 | 2018-10-23 | 大亚人造板集团有限公司 | A kind of outdoor version fibre board use modified urea-formaldehyde resin adhesive and preparation method thereof |
CN107118722A (en) * | 2017-05-27 | 2017-09-01 | 柳州市鹏森木业加工有限公司 | A kind of wood-based plate urea-formaldehyde resin adhesive and its preparation technology |
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