CN109337622A - A kind of modified urea-formaldehyde resin adhesive and preparation method thereof - Google Patents
A kind of modified urea-formaldehyde resin adhesive and preparation method thereof Download PDFInfo
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- CN109337622A CN109337622A CN201811229112.9A CN201811229112A CN109337622A CN 109337622 A CN109337622 A CN 109337622A CN 201811229112 A CN201811229112 A CN 201811229112A CN 109337622 A CN109337622 A CN 109337622A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09J161/32—Modified amine-aldehyde condensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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- Chemical Kinetics & Catalysis (AREA)
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- Phenolic Resins Or Amino Resins (AREA)
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Abstract
The invention discloses a kind of modified urea-formaldehyde resin adhesives and preparation method thereof, number scale by weight, it include 100 ~ 110 parts of 37% formalin of volume fraction, 15 ~ 20 parts of lactide solid, 100 parts of urea, 8 ~ 16 parts of EDTA solid, 30 ~ 50 parts of 2- chlorobenzene amine aqueous solution in the adhesive.The modified urea-formaldehyde resin adhesive is prepared using traditional " alkali-Acid-Base " flow process, promote the steady progress of reaction as acidic catalyst using EDTA during the preparation process, and the usage amount of formaldehyde is reduced by addition lactide and 2- chloroaniline, the content of free formaldehyde is reduced, while enhancing the viscosity, water resistance and ageing-resistant performance of adhesive.The preparation process basic procedure of modified urea-formaldehyde resin adhesive and prior art are close in the present invention, and simple process is easy to operate, without being transformed to existing equipment.
Description
Technical field
The present invention relates to the technical fields of wood adhesive, and in particular to a kind of modified urea-formaldehyde resin adhesive and its preparation
Method.
Background technique
In building materials, in use, Lauxite has, solidification process is rapid, bonding timber intensity is higher, production operation is convenient,
The advantages that raw material are cheap and rich and easy to get, rapidly developing it becomes the maximum product of world today's wood adhesive dosage
Kind, occupy 80% or more of wood adhesive product population.But Lauxite itself also has the shortcomings that, as wet-heat resisting is steady
It is qualitative it is poor, content of free aldehyde is higher etc., the disadvantage of Lauxite maximum is exactly that can gradually release in its bonding later period for being used for wood-based plate
Put formaldehyde.
Chinese patent CN201210037079.6 discloses a kind of Lauxite produced using amino acid as formaldehyde catching agent
Glue and preparation method thereof, with the one or more of glycine, leucine, isoleucine, valine, phenylalanine, glutamic acid
Mixture is that formaldehyde catching agent produces Lauxite；Application No. is CN201410384826.2 disclose it is a kind of cottonseed protein modified
Urea-formaldehyde resin adhesive powder is blended with Lauxite using cottonseed protein and prepares modified urea-formaldehyde resin glue powder, and existing ureaformaldehyde is solved
There is long-term release formaldehyde in use process in resin adhesive.
The artificial board Form aldehyde release of urea-formaldehyde resin adhesive bonding is a long-term and slow process, by resin
Formaldehyde catching agent is added during synthesis early period and later period impregnation of adhesive, solidified resin can be reduced quickly in a short time
Free formaldehyde discharge, but subsequent formaldehyde emissions are primarily due to the unreasonable of resin structure, even if using physical absorption
The formaldehyde catching agent of type, also can be ineffective when absorption reaches balance.If undoubtedly will using a large amount of formaldehyde catching agent
Lead to the rising of cost.
Summary of the invention
In view of the deficiencies of the prior art, the invention discloses a kind of modified urea-formaldehyde resin adhesives and preparation method thereof, originally
Modified urea-formaldehyde resin adhesive in invention is prepared, is adopted during the preparation process using traditional " alkali-Acid-Base " flow process
It uses EDTA to promote the steady progress of reaction as acidic catalyst, and making for formaldehyde is reduced by addition lactide and 2- chloroaniline
Dosage, reduces the content of free formaldehyde, while enhancing the viscosity, water resistance and ageing-resistant performance of adhesive, using party's legal system
The standby adhesive obtained can be applied to the adhesive of glued board.
Technical scheme is as follows:
A kind of modified urea-formaldehyde resin adhesive, by weight number scale, it is molten comprising 37% formaldehyde of volume fraction in the adhesive
100~110 parts of liquid, 15~20 parts of lactide solid, 100 parts of urea, 8~16 parts of EDTA solid, 2- chlorobenzene amine aqueous solution 30~50
Part.
As a further explanation of the present invention, modified urea-formaldehyde resin adhesive preparation method the following steps are included:
(1) load weighted formalin is added in reaction vessel, and be stirred continuously, using 30% sodium hydroxide solution tune
Saving solution ph is 7.1~7.5；
(2) first urea is added, lactide solid is added, is kept the temperature after heating；
(3) 80~82 DEG C are cooled to, adjusting pH value of solution is 7.0~7.5, and second batch urea is added and is reacted；
(4) EDTA solid is added, and adjusts pH value to being kept the temperature after 4.5~5.0；
(5) pH value 7.5~8.0 is adjusted, and is cooled to 70 DEG C；
(6) third batch urea is added, 2- chlorobenzene amine aqueous solution is added, is then reacted；
(7) cooling down and adjusting solution ph is 7.0~7.5, is discharged after cooling.
As a further explanation of the present invention: three batches of urea additional amounts are respectively 60 parts, 15 parts, 25 parts.
As a further explanation of the present invention: heat-retaining condition is to make solution temperature with 25~45min after heating in step (2)
87~90 DEG C are risen to, 25~40min is then kept the temperature.
As a further explanation of the present invention: be added in step (3) condition that second batch urea is reacted be with 15~
20min is warming up to 20~30min of insulation reaction at 88~95 DEG C.
As a further explanation of the present invention: in step (4) holding temperature be 88~92 DEG C, soaking time be 25~
30min。
As a further explanation of the present invention: 2- chlorobenzene amine aqueous solution being added in step (6), the condition then reacted is
30~40min is reacted at 65~70 DEG C.
As a further explanation of the present invention: the temperature to discharge after cooling in step (7) is 35 DEG C or less.
Technical principle of the invention is as follows:
Ketone group and two methyl polymerize in 60 DEG C or more easily polymerizations with formaldehyde and urea containing there are two in lactide structure
Macromolecule polyalcohol is formed, is added at the synthesis initial stage of Lauxite, it can also be in the addition reaction of alkali stage, with hydroxyl first
Base urea combines, and reduces methylolurea reversible reaction and generates formaldehyde, to reduce the content of free formaldehyde.
Suitable catalyst can improve the bonding property of Lauxite, and urging for corresponding properties is added under condition of different pH
Agent can be such that reacting balance carries out.EDTA be dissolved in it is weakly acidic in solution, adjust solution ph while, promote reaction
It is steady to carry out, reduce the production quantity of formaldehyde in reversible reaction.Meanwhile EDTA is backbone, is contained in two edge tail of structure
Hydroxyl can be reacted with methylolurea, to introduce backbone, increase the bridging property of Lauxite, to increase adhesive
Viscosity.
There are phenyl ring and amino, therefore certain properties with phenyl ring and amino in 2- chlorobenzene amine structure.2- chloroaniline knot
Amino in structure is strong electron donating group, increases the cloud density on phenyl ring, therefore it is anti-that parental materials easily occur on phenyl ring
Answer, be easy reacted with Lauxite in product react, to introduce phenyl ring in adhesive, improve the stabilization of adhesive
Property, while significantly improving the water resistance and ageing-resistant performance of adhesive.
Beneficial effects of the present invention:
Urea-formaldehyde resin adhesive in the present invention reduces the additive amount of formaldehyde, and by structurally-modified, forms more
Stable cross-linked structure reduces the burst size of formaldehyde, to reduce the harm of free formaldehyde when wood-based plate makes, and this hair
Bright middle preparation method technique is close with prior art processes process, easy to operate, does not need to be transformed existing equipment, used
The cost of material is low, reduces the production cost.
Specific embodiment
Embodiment 1:
A kind of modified urea-formaldehyde resin adhesive, by weight number scale, it is molten comprising 37% formaldehyde of volume fraction in the adhesive
100 parts of liquid, 15 parts of lactide solid, 100 parts of urea, 8 parts of EDTA solid, 30 parts of 2- chlorobenzene amine aqueous solution, preparation step is as follows:
(1) it in the 100 parts of addition reaction vessels of formalin for being 37% by load weighted volume fraction, and is stirred continuously,
30% sodium hydroxide solution is used to adjust solution ph as 7.1~7.5；
(2) 60 parts of urea are added, lactide solid is added, additional amount is 15 parts, and heating is made on solution temperature with 25min
87~90 DEG C are risen to, 25min is then kept the temperature；
(3) 80~82 DEG C are cooled to, adjusting pH value of solution is 7.0~7.5, and second batch urea is added, and additional amount is 15 parts, is used
15min is warming up at 88~95 DEG C and keeps the temperature 20min；
(4) 8 parts of EDTA solid are added, and adjusting pH value is 4.5~5.0, keeps the temperature 25min at 88~92 DEG C；
(5) pH value 7.5~8.0 is adjusted, and is cooled to 70 DEG C；
(6) third batch urea is added, additional amount is 25 parts, and 30 parts of 2- chlorobenzene amine aqueous solution is added, reacts at 65~70 DEG C
30min；
(7) cooling down and adjusting solution ph is 7.0~7.5, is cooled to 35 DEG C with bottom discharge.
Embodiment 2:
A kind of modified urea-formaldehyde resin adhesive, by weight number scale, it is molten comprising 37% formaldehyde of volume fraction in the adhesive
105 parts of liquid, 17 parts of lactide solid, 100 parts of urea, 16 parts of EDTA solid, 40 parts of 2- chlorobenzene amine aqueous solution, preparation step is as follows:
(1) it in the 105 parts of addition reaction vessels of formalin for being 37% by load weighted volume fraction, and is stirred continuously,
30% sodium hydroxide solution is used to adjust solution ph as 7.1~7.5；
(2) 60 parts of urea are added, lactide solid is added, additional amount is 17 parts, and heating is made on solution temperature with 45min
87~90 DEG C are risen to, 40min is then kept the temperature；
(3) 80~82 DEG C are cooled to, adjusting pH value of solution is 7.0~7.5, and second batch urea is added, and additional amount is 15 parts, is used
20min is warming up at 88~95 DEG C and keeps the temperature 30min；
(4) 16 parts of EDTA solid are added, and adjusting pH value is 4.5~5.0, keeps the temperature 35min at 88~92 DEG C；
(5) pH value 7.5~8.0 is adjusted, and is cooled to 70 DEG C；
(6) third batch urea is added, additional amount is 25 parts, and 40 parts of 2- chlorobenzene amine aqueous solution is added, reacts at 65~70 DEG C
40min；
(7) cooling down and adjusting solution ph is 7.0~7.5, is cooled to 30 DEG C with bottom discharge.
Embodiment 3:
A kind of modified urea-formaldehyde resin adhesive, by weight number scale, it is molten comprising 37% formaldehyde of volume fraction in the adhesive
110 parts of liquid, 19 parts of lactide solid, 100 parts of urea, 10 parts of EDTA solid, 50 parts of 2- chlorobenzene amine aqueous solution, preparation step is as follows:
(1) it in the 110 parts of addition reaction vessels of formalin for being 37% by load weighted volume fraction, and is stirred continuously,
30% sodium hydroxide solution is used to adjust solution ph as 7.1~7.5；
(2) 60 parts of urea are added, lactide solid is added, additional amount is 19 parts, and heating is made on solution temperature with 35min
87~90 DEG C are risen to, 30min is then kept the temperature；
(3) 80~82 DEG C are cooled to, adjusting pH value of solution is 7.0~7.5, and second batch urea is added, and additional amount is 15 parts, is used
18min is warming up at 88~95 DEG C and keeps the temperature 25min；
(4) 10 parts of EDTA solid are added, and adjusting pH value is 4.5~5.0, keeps the temperature 30min at 88~92 DEG C；
(5) pH value 7.5~8.0 is adjusted, and is cooled to 70 DEG C；
(6) third batch urea is added, additional amount is 25 parts, and 50 parts of 2- chlorobenzene amine aqueous solution is added, reacts at 65~70 DEG C
35min；
(7) cooling down and adjusting solution ph is 7.0~7.5, is cooled to 35 DEG C with bottom discharge.
Embodiment 4:
A kind of modified urea-formaldehyde resin adhesive, by weight number scale, it is molten comprising 37% formaldehyde of volume fraction in the adhesive
108 parts of liquid, 20 parts of lactide solid, 100 parts of urea, 14 parts of EDTA solid, 38 parts of 2- chlorobenzene amine aqueous solution, preparation step is as follows:
(1) it in the 108 parts of addition reaction vessels of formalin for being 37% by load weighted volume fraction, and is stirred continuously,
30% sodium hydroxide solution is used to adjust solution ph as 7.1~7.5；
(2) 60 parts of urea are added, lactide solid is added, additional amount is 20 parts, and heating is made on solution temperature with 40min
87~90 DEG C are risen to, 37min is then kept the temperature；
(3) 80~82 DEG C are cooled to, adjusting pH value of solution is 7.0~7.5, and second batch urea is added, and additional amount is 15 parts, is used
19min is warming up at 88~95 DEG C and keeps the temperature 25min；
(4) 14 parts of EDTA solid are added, and adjusting pH value is 4.5~5.0, keeps the temperature 30min at 88~92 DEG C；
(5) pH value 7.5~8.0 is adjusted, and is cooled to 70 DEG C；
(6) third batch urea is added, additional amount is 25 parts, and 38 parts of 2- chlorobenzene amine aqueous solution is added, reacts at 65~70 DEG C
38min；
(7) cooling down and adjusting solution ph is 7.0~7.5, is cooled to 31 DEG C with bottom discharge.
Embodiment 5:
Modified urea-formaldehyde resin adhesive performance detection
Free formaldehyde content is according to GB 18583- in the urea-formaldehyde resin adhesive prepared in embodiment 1,2,3,4
2008 are measured, and adhesive viscosity measurement is using II type viscosmeter of DV- (Brookfield company of the U.S.) under the conditions of 25 DEG C
It measures.Free formaldehyde content, viscosity measurement are as shown in table 1:
The Lauxite viscosity and free formaldehyde content testing result that 1 embodiment 1-4 of table is obtained
As table 1 it is recognised that adhesivity is strong, free formaldehyde using the viscosity stabilized of Lauxite prepared by the present invention
Content is near 0.13, and much smaller than 0.5% specified in GB 18583-2008, free formaldehyde content has obtained good control.
Embodiment 6:
Modified urea-formaldehyde resin adhesive application
The urea-formaldehyde resin adhesive that embodiment 1 is obtained is main adhesive proteins, and beech, dragon spruce mixing wood shavings are wood
Material adds the ammonium chloride of adhesive quality 1% as curing agent, and 22% flour modulates adhesive as filler, and use is two-sided
Sizing, resin added are 290~310g/m2, it is conventionally hot-forming, it is made as the slab of 350 × 300mm, formaldehyde is released
It is high-volume measured according to national standard GB/T 23825-2009, purchase is common on the market to can be used for indoor E1 grade urea-formaldehyde resin
For particieboard as control, measurement result is as shown in table 2.
2 particieboard burst size of methanal measurement result of table
As shown in Table 2, commercially available wood shavings are lower than using the particieboard burst size of methanal of Lauxite prepared by the present invention production
Plate reaches E1 grades, can be directly used for interior.
Claims (8)
1. a kind of modified urea-formaldehyde resin adhesive, it is characterised in that: number scale by weight includes volume fraction in the adhesive
37% 100 ~ 110 parts of formalin, 15 ~ 20 parts of lactide solid, 100 parts of urea, 8 ~ 16 parts of EDTA solid, 2- chlorobenzene amine aqueous solution
30 ~ 50 parts.
2. a kind of modified urea-formaldehyde resin adhesive according to claim 1, which is characterized in that preparation method includes following step
It is rapid:
(1) load weighted formalin is added in reaction vessel, and be stirred continuously, adjusted using 30% sodium hydroxide solution molten
Liquid pH value is 7.1 ~ 7.5；
(2) first urea is added, lactide solid is added, is kept the temperature after heating；
(3) 80 ~ 82 DEG C are cooled to, adjusting pH value of solution is 7.0 ~ 7.5, and second batch urea is added and is reacted；
(4) EDTA solid is added, and adjusts pH value to being kept the temperature after 4.5 ~ 5.0；
(5) pH value 7.5 ~ 8.0 is adjusted, and is cooled to 70 DEG C；
(6) third batch urea is added, 2- chlorobenzene amine aqueous solution is added, is then reacted；
(7) cooling down and adjusting solution ph is 7.0 ~ 7.5, is discharged after cooling.
3. a kind of preparation method of modified urea-formaldehyde resin adhesive according to claim 2, it is characterised in that: three batches of urea add
Entering amount is respectively 60 parts, 15 parts, 25 parts.
4. a kind of preparation method of modified urea-formaldehyde resin adhesive according to claim 2, it is characterised in that: in step (2)
Heat-retaining condition is so that solution temperature is risen to 87 ~ 90 DEG C with 25 ~ 45min after heating, then keeps the temperature 25 ~ 40min.
5. a kind of preparation method of modified urea-formaldehyde resin adhesive according to claim 2, it is characterised in that: in step (3)
It is to be warming up to 20 ~ 30min of insulation reaction at 88 ~ 95 DEG C with 15 ~ 20min that the condition that second batch urea is reacted, which is added,.
6. a kind of preparation method of modified urea-formaldehyde resin adhesive according to claim 2, it is characterised in that: in step (4)
Holding temperature is 88 ~ 92 DEG C, and soaking time is 25 ~ 30min.
7. a kind of preparation method of modified urea-formaldehyde resin adhesive according to claim 2, it is characterised in that: in step (6)
2- chlorobenzene amine aqueous solution is added, the condition then reacted is that 30 ~ 40min is reacted at 65 ~ 70 DEG C.
8. a kind of preparation method of modified urea-formaldehyde resin adhesive according to claim 2, it is characterised in that: in step (7)
The temperature to discharge after cooling is 35 DEG C or less.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811229112.9A CN109337622A (en) | 2018-10-22 | 2018-10-22 | A kind of modified urea-formaldehyde resin adhesive and preparation method thereof |
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| CN201811229112.9A CN109337622A (en) | 2018-10-22 | 2018-10-22 | A kind of modified urea-formaldehyde resin adhesive and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103468185A (en) * | 2013-09-27 | 2013-12-25 | 徐州安联木业有限公司 | Formula and preparation method of urea-formaldehyde resin adhesive for glued board |
| JP2014524503A (en) * | 2011-08-19 | 2014-09-22 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing condensation resin and use of the condensation resin |
| CN105001819A (en) * | 2015-07-03 | 2015-10-28 | 金爱莲 | Modified urea-formaldehyde resin, and preparation method and applications thereof |
| CN105585993A (en) * | 2016-03-11 | 2016-05-18 | 广西大学 | Method for preparing isobutyl aldehyde modified urea-formaldehyde resin adhesive |
-
2018
- 2018-10-22 CN CN201811229112.9A patent/CN109337622A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014524503A (en) * | 2011-08-19 | 2014-09-22 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing condensation resin and use of the condensation resin |
| CN103468185A (en) * | 2013-09-27 | 2013-12-25 | 徐州安联木业有限公司 | Formula and preparation method of urea-formaldehyde resin adhesive for glued board |
| CN105001819A (en) * | 2015-07-03 | 2015-10-28 | 金爱莲 | Modified urea-formaldehyde resin, and preparation method and applications thereof |
| CN105585993A (en) * | 2016-03-11 | 2016-05-18 | 广西大学 | Method for preparing isobutyl aldehyde modified urea-formaldehyde resin adhesive |
Non-Patent Citations (1)
| Title |
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| 余海帆: "脲醛树脂改性研究", 《中国优秀博硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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