CN102604575B - Modified urea formaldehyde adhesive and preparation method thereof - Google Patents
Modified urea formaldehyde adhesive and preparation method thereof Download PDFInfo
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- CN102604575B CN102604575B CN 201210092963 CN201210092963A CN102604575B CN 102604575 B CN102604575 B CN 102604575B CN 201210092963 CN201210092963 CN 201210092963 CN 201210092963 A CN201210092963 A CN 201210092963A CN 102604575 B CN102604575 B CN 102604575B
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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. Thefree 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 the gas of volatilization 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%, still, have the stable low of glue again, storage time is short, does not have precompressed in the course of processing, makes the glued board quality low, thereby increase labour intensity, be unfavorable for the raising of working efficiency, and there is the danger of solidifying in existing urea-formaldehyde glue in the impregnation process, be lower than 4.6 such as pH when the impregnation, just have the phenomenon of curing.
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 polyvinyl alcohol are made 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 polyvinyl alcohol;
Two, the quality percentage composition that step 1 is taken by weighing is that 37% formaldehyde adds in the reactor, heat temperature raising, when the pressure of boiler reaches 0.3MPa, when the formaldehyde temperature in the reactor reaches 30 ℃～35 ℃, be that 25%～30% caustic soda solution is regulated formaldehyde pH to 7.5～8.0 with concentration, add the sodium cellulosate that step 1 takes by weighing again;
When three, continuing to be heated to formaldehyde temperature in the reactor and reach 36 ℃～40 ℃, be that 25%～30% caustic soda solution is regulated formaldehyde pH to 8.0 with concentration, 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 ℃, boiler pressure stops heating when being 1.5～2.0MPa, be warming up to 92 ℃ by reactor self heat release, 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 gets mixed solution;
Five, adopting concentration is pH of mixed to 4.8～5.0 that 25%～28% ammonium chloride solution regulating step four obtains, mixed solution is added drop-wise to when observing to reaction end in 8～10 ℃ of water, be that 25%～30% caustic soda solution is regulated pH of mixed to 6.7～7.2 with concentration again, the urea that adds 90～100 weight parts again, mixed 10～20 minutes, mixed solution is cooled to 70 ℃, the urea that adds 10～20 weight parts then, the phenol that step 1 takes by weighing, ammoniacal liquor and trimeric cyanamide, after stirring, when mixed solution is cooled to 40 ℃, be that 25%～30% caustic soda solution is regulated pH of mixed value to 7.5～8.5 with concentration again, put glue, namely get urea-formaldehyde glue; Described reaction reaches terminal point and refers to record viscosity and reach 25～30 seconds with being coated with-4 glasss/and 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 of glue, makes content of free aldehyde be down to very low value, and free formaldehyde content is lower than 0.1% in the urea-formaldehyde glue of the present invention.
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 is in the actual course of processing, add polyvinyl alcohol, make the precompressed raising of glued board, compare the glued board of present no precompressed, can improve the quality of glued board, owing to carry out precompressed in advance, therefore, can save working efficiency, have problems such as skew when avoiding because of the compacting glued board, influence working efficiency.
Embodiment
Technical solution 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 present 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 polyvinyl alcohol are made 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 present embodiment can further reduce formaldehyde content, the phenol that adds can make glue can further increase the hot water of glue, make content of free aldehyde be down to very low value, free formaldehyde content is lower than 0.1% in the present embodiment urea-formaldehyde glue.
Sodium cellulosate in the urea-formaldehyde glue of present 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 present embodiment is in the actual course of processing, add polyvinyl alcohol, make the precompressed raising of glued board, compare the glued board of present no precompressed, can improve the quality of glued board, owing to carry out precompressed in advance, therefore, can save working efficiency, have problems such as skew when avoiding because of the compacting glued board, influence working efficiency.
Embodiment two: what present 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 polyvinyl alcohol 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 present 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 polyvinyl alcohol;
Two, the quality percentage composition that step 1 is taken by weighing is that 37% formaldehyde adds in the reactor, by the boiler heat temperature raising, when the pressure of boiler reaches 0.3 MPa, when the formaldehyde temperature in the reactor reaches 30 ℃～35 ℃, be that 25%～30% caustic soda solution is regulated formaldehyde pH to 7.5～8.0 with concentration, add the sodium cellulosate that step 1 takes by weighing again;
When three, continuing to be heated to formaldehyde temperature in the reactor and reach 36 ℃～40 ℃, be that 25%～30% caustic soda solution is regulated formaldehyde pH to 8.0 with concentration, 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 ℃, boiler pressure stops heating when being 1.5～2.0MPa, be warming up to 92 ℃ by reactor self heat release, 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 gets mixed solution;
Five, adopting concentration is pH of mixed to 4.8～5.0 that 25%～28% ammonium chloride solution regulating step four obtains, mixed solution is added drop-wise to when observing to reaction end in 8～10 ℃ of water, be that 25%～30% caustic soda solution is regulated pH of mixed to 6.7～7.2 with concentration again, the urea that adds 90～100 weight parts again, mixed 10～20 minutes, mixed solution is cooled to 70 ℃, the urea that adds 10～20 weight parts then, the phenol that step 1 takes by weighing, ammoniacal liquor and trimeric cyanamide, after stirring, when mixed solution is cooled to 40 ℃, be that 25%～30% caustic soda solution is regulated pH of mixed value to 7.5～8.5 with concentration again, put glue, namely get urea-formaldehyde glue; Described reaction reaches terminal point and refers to record viscosity and reach 25～30 seconds with being coated with-4 glasss/and 25 ℃.
The ammoniacal liquor that adds in the urea-formaldehyde glue of present embodiment can further reduce formaldehyde content, the phenol that adds can make glue can further increase the hot water of glue, make content of free aldehyde be down to very low value, free formaldehyde content is lower than 0.1% in the present embodiment urea-formaldehyde glue.
Sodium cellulosate in the urea-formaldehyde glue of present 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 present embodiment is in the actual course of processing, add polyvinyl alcohol, make the precompressed raising of glued board, compare the glued board of present no precompressed, can improve the quality of glued board, owing to carry out precompressed in advance, therefore, can save working efficiency, have problems such as skew when avoiding because of the compacting glued board, influence working efficiency.
Specifically be embodiment four: what present embodiment and embodiment three were different is: the formaldehyde temperature in the described reactor of step 2 is 32 ℃～34 ℃.Other step and parameter are identical with step 3.
Specifically be embodiment five: what present 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 polyvinyl alcohol.Other step and parameter are identical with step 3 to four.
Specifically be embodiment six: what present 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 present 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 present 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 present 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, is that 25%～30% caustic soda solution is regulated pH of mixed to 7.0 with concentration again.Other step and parameter are identical with one of step 3 to eight.
Specifically be embodiment ten: what present embodiment was different with one of embodiment three to eight is: step 5 is described when mixed solution is cooled to 40 ℃, is that 25%～30% caustic soda solution is regulated pH of mixed value to 7.8～82 with concentration again.Other step and parameter are identical with one of step 3 to eight.
By 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 polyvinyl alcohol 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 reactor, and heat temperature raising when reactor pressure reaches 0.3Mpa, when temperature is 35 ℃, is 25% caustic soda solution adjusting formaldehyde pH to 8.0 with concentration, adds the sodium cellulosate that step 1 takes by weighing again;
Three, continuing reacting by heating still to 40 ℃, is after 25% caustic soda solution is regulated pH to 8.0 with concentration, adds the urea of 214kg first, mixes, and gets and just mixes liquid, and adopting concentration is that 25% caustic soda solution is regulated 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, is warming up to 92 ℃ by self heat release, and adopting concentration is that 25% caustic soda solution is regulated pH to 6.5, and insulation reaction 30 minutes gets 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, observation reaches reaction end, record viscosity and reach 25～30 seconds with being coated with-4 glasss/8 ℃, be that 25% caustic soda solution is regulated pH to 7.2 with concentration again, the urea that adds 99kg again, mixed 15 minutes, mixed solution is cooled to 70 ℃, the urea that adds 20kg then, the phenol that step 1 takes by weighing and trimeric cyanamide, after stirring, when mixed solution is continued to be cooled to 40 ℃, be that 25% caustic soda solution is regulated pH of mixed value to 8.0 with concentration, put glue, namely get 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; Free formaldehyde content is lower than 0.1% in the urea-formaldehyde glue that this test obtains.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 polyvinyl alcohol are made 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 polyvinyl alcohol 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 polyvinyl alcohol;
Two, the quality percentage composition that step 1 is taken by weighing is that 37% formaldehyde adds in the reactor, by the boiler heat temperature raising, when the pressure of boiler reaches 0.3MPa, when the formaldehyde temperature in the reactor reaches 30 ℃～35 ℃, be that 25%～30% caustic soda solution is regulated formaldehyde pH to 7.5～8.0 with concentration, add the sodium cellulosate that step 1 takes by weighing again;
When three, continuing to be heated to formaldehyde temperature in the reactor and reach 36 ℃～40 ℃, be that 25%～30% caustic soda solution is regulated formaldehyde pH to 8.0 with concentration, 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 ℃, boiler pressure stops heating when being 1.5～2.0MPa, be warming up to 92 ℃ by reactor self heat release, 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 gets mixed solution;
Five, adopting concentration is pH of mixed to 4.8～5.0 that 25%～28% ammonium chloride solution regulating step four obtains, mixed solution is added drop-wise to when observing to reaction end in 8～10 ℃ of water, be that 25%～30% caustic soda solution is regulated pH of mixed to 6.7～7.2 with concentration again, the urea that adds 90～100 weight parts again, mixed 10～20 minutes, mixed solution is cooled to 70 ℃, the urea that adds 10～20 weight parts then, the phenol that step 1 takes by weighing, ammoniacal liquor and trimeric cyanamide, after stirring, when mixed solution is cooled to 40 ℃, be that 25%～30% caustic soda solution is regulated pH of mixed value to 7.5～8.5 with concentration again, put glue, namely get urea-formaldehyde glue; Described reaction reaches terminal point and refers to record viscosity and reach 25～30 seconds with being coated with-4 glasss/and 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 reactor 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 polyvinyl alcohol.
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, is that 25%～30% caustic soda solution is regulated pH of mixed to 7.0 with concentration again.
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 ℃, is that 25%～30% caustic soda solution is regulated pH of mixed value to 7.8～8.2 with concentration again.
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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 |
| CN103555241B (en) * | 2013-11-22 | 2015-02-04 | 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 |
| 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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| CN1461786A (en) * | 2002-05-31 | 2003-12-17 | 汪正红 | Manufacturing method of environmental protection type urea-formaldehyde resin glue |
| CN101200549B (en) * | 2007-12-04 | 2010-12-22 | 中国林业科学研究院木材工业研究所 | Method for preparing modified urea-formaldehyde resin powder material |
| CN101265314A (en) * | 2008-04-30 | 2008-09-17 | 北京化工大学 | Environmental protection urea-formaldehyde resin and preparation method thereof |
| CN102086295B (en) * | 2010-06-28 | 2013-05-08 | 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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