CN103382376A - Treatment method of TGIC by-product and utilization method for obtaining adhesion agent by utilizing same - Google Patents
Treatment method of TGIC by-product and utilization method for obtaining adhesion agent by utilizing same Download PDFInfo
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Abstract
The invention discloses an efficient utilization method of a triglycidyl isocyanurate (TGIC) by-product. The method employs a small amount of urea to undergo a reaction with epoxy groups of the TGIC by-product, so that the epoxy groups of the by-product are converted into hydroxyl groups, simultaneously the molecular weight of the by-product is increased, and thus a reaction product can be used as an adhesion agent; the reaction product contains no formaldehyde and has the adhesive strength which can meet use requirements, so the reaction product is more healthy and environmentally friendly. After testing, a paper laminated board pressed by the adhesion agent has the water resistance performance which is equal to that of a urea-formaldehyde resin adhesive laminated board, and has the strength which is superior to that of the urea-formaldehyde resin adhesive laminated board.
Description
Technical field
The invention belongs to desulfurization and recycle the field, relate to a kind of utilize triglycidyl isocyanurate by product and urea to prepare novel non-formaldehyde glue additive method, this of preparation can be used for decorating with veneer sheet plate sandwich layer Resin adhesive without the aldehyde glue additive.
Background technology
Owing to comparing with wood-based planet, paper-based laminate has the series of advantages such as cost is low, intensity is high, wear resistance is good, moistureproof, therefore is widely used.Decorating is by certain Resin adhesive, paper to be flooded with veneer sheet, the sheet material that is glued together and is cured moulding again and obtains.Widely used veneer sheet sandwich layer Resin adhesive is urea-formaldehyde resin adhesive in the market.
In the urea-formaldehyde resin building-up process, the suitable proportion of formaldehyde and urea is generally at 1.1 ~ 1.5:1.But in order to guarantee good bond effect, in actual use procedure, producer often makes formaldehyde greatly excessive.The complete formaldehyde of unreacted can discharge in veneer sheet making and use procedure, and environment and workman, user's health are caused disadvantageous effect.Therefore, low content of free formaldehyde or formaldehyde-free resins glue are the important development directions that hard board is used glue.
Triglycidyl isocyanurate (TGIC is commonly called as " dai serge gram ") is the linking agent that is mainly used in powder coating.Produce in the process of TGIC under the prior art condition, inevitably can obtain the mixture that some contain the chlorinated isocyanurates structural compounds of at least two hydroxyls or two epoxy group(ing), the crystal property of they and TGIC is different, therefore by after crystallization extracts TGIC in methyl alcohol, these by products just are dissolved in methyl alcohol.TGIC by product effective constituent chemical structural formula is as follows:
With 10000 tons of calculating of annual production of national TGIC, every year all can the reluctant by product of output more than 5000 tons.Existing producer is substantially all direct burning disposal or the burning indirectly that acts as a fuel, and has brought certain problem of environmental pollution.Manufacturer never has good way for the comprehensive utilization of TGIC by product.
Constructional feature and chemical physics performance according to the TGIC by product, Tian Zhihong is in the document (application of TGIC by product in the paper composite adhesive, HeFei University of Technology, 2010) in, report is by modification can obtain a kind of paper-plastic composite adhesive to the TGIC by product, but use tolylene diisocyanate in producing, be unfavorable for producing and promote so its toxicity is large, cost is higher; Wang Yu report in document (application of TGIC by product in thermosol, HeFei University of Technology, 2011) obtains a kind of thermosol by adding oxidation inhibitor modification TGIC by product, but its production process is complicated.
Summary of the invention
The object of the invention is to use a small amount of urea and TGIC byproduct reaction, generate and mainly contain hydroxyl and the amino novel non-formaldehyde tackiness agent consistent with urea-formaldehyde resin functional group in a kind of chemical structure, because it does not contain formaldehyde and cohesive strength can satisfy service requirements, therefore more healthy, environmental protection.
The technical solution used in the present invention is for this reason:
Described by product has following chemical structural formula:
Carry out according to following steps:
1) TGIC by product and urea are added in reaction vessel, in 75 ℃ ~ 95 ℃ reflux condensation mode reaction 2 ~ 4h;
2) product that obtains is adjusted to 30% ~ 45% with solid content, with urea-formaldehyde resin by 1 ︰ 4～2 ︰ 3(mass ratioes) mix and obtain sizing agent.
Wherein 1) in step: the solid content of described TGIC by product is 50% ~ 60%, and the oxirane value scope is 0.4 ~ 0.6;
The TGIC by product is scaled the rear Fu Chan of TGIC of solid content 100% Wu ︰ urea (mol ratio)=2 ︰ 1～5 ︰ 1.
Wherein 2) solid content of the urea-formaldehyde resin described in step is 40%-45%, obtains faint yellow translucent liquid, and solid content is 49%-53%, and year is 12 mPas～23 mPas.
Sizing agent utilize method, use above-mentioned sizing agent that the special-purpose kraft paper of veneer sheet is flooded, after dipping, kraft paper is placed in 120 ℃～130 ℃ baking oven Procuring and obtained prepreg in 10～15 minutes, prepreg is placed on the thermocompressor of 110 ℃ ~ 180 ℃ press curing 10min ~ 60min under 10 ~ 50MPa, obtains paper-based laminate.
Described dipping glue amount is controlled at 0.008 g/cm
2～0.011 g/cm
2
Described pressing plate process: first with press and mould in 100 ℃ of preheating 2min, afterwards several prepregs are put into mould, compression moulding under the pressure of setting, temperature and time.
The present invention utilizes the epoxide group in TGIC by product chemical structure, by product and a small amount of urea are reacted under suitable condition (the reaction needed temperature of considering hydroxyl and epoxide group is higher), make the epoxy group(ing) of by product be converted into hydroxyl, increase simultaneously the molecular weight of by product, reaction principle is as follows:
Mainly contain hydroxyl and amino in reacted product, consistent with the functional group in urea-formaldehyde resin, can be effectively and urea-formaldehyde resin react to each other.
The present invention has following advantage and beneficial effect:
1. the veneer sheet that the TGIC by product can be converted into than high added value by simple technique sticks with glue the agent product.
2. this kind sizing agent does not contain formaldehyde, outside dewatering, there is no other volatile component, environmental friendliness, and cost is low, and stability in storage is good.After this kind sizing agent and urea-formaldehyde resin are used in conjunction with, can effectively reduce the laminated board production cost, improve simultaneously tensile property and the water resistance of sheet material.
3. this kind filled up the efficient technological gap that utilizes of domestic TGIC by product without the development of aldehyde sizing agent.
Embodiment
The TGIC by product that following examples adopt comes from Yangzhou Sandeli Chemical Co., Ltd., and solid content is 50% ~ 60%, the oxirane value scope is 0.4 ~ 0.6 the aqueous solution,
Urea is the analytical reagent that Shanghai Ling Feng chemical reagent factory is produced,
Rotational viscosimeter used: model NDJ-79, Shanghai Changji Geological Instrument Co., Ltd., the vulcanizing press that uses is 25t vulcanizing press: model QLB-350 * 350 * 2, rubber machinery plant, Shanghai.
Embodiment 1:
Add 4kg(8.7mol in the reaction unit that thermometer, reflux condensation mode and whipping appts are housed) the TGIC by product, be heated to 80 ℃ and under agitation add 174.1g(2.9mol) urea, react 2h under 80 ℃.Reaction obtains faint yellow transparent products after finishing, and the solid content of product is 51.25%, and viscosity is 12.5 mPas.With product solid content modulation 42%, with urea-formaldehyde resin by 3 ︰ 7(mass ratioes) mix and obtain sizing agent.
Then kraft paper is carried out impregnation, compression molding, its process is: use sizing agent that the special-purpose kraft paper of veneer sheet is flooded, dipping glue amount 0.008 g/cm
2, after dipping, kraft paper is placed in 130 ℃ of baking oven Procuring and obtained prepreg in 10 minutes, then carries out pressing plate: prepreg is placed on the thermocompressor of 180 ℃ press curing 30min under 10MPa, obtains paper-based laminate.
According to " Test methods of evaluating the properties of woodbased panels and surface decorated woodbased panels " GB/T 17657-1999, veneer sheet is placed in boiling water and boils 2h, obtain test result: plate surfacing, without bubbling but slightly layering, rate of body weight gain 15.83% thickens rate 12.94%.
Embodiment 2:
Add 4.6kg(9.3mol in the reaction unit that thermometer, reflux condensation mode and whipping appts are housed) the TGIC by product, be heated to 75 ℃ and under agitation add 174.1g(2.9mol) urea, react 4h under 75 ℃.Reaction obtains faint yellow transparent products after finishing, and the solid content of product is 51.70%, and viscosity is 16.5 mPas.With product solid content modulation 45%, with solid content be that 42% urea-formaldehyde resin is by 1 ︰ 3(mass ratio) mix and obtain sizing agent.
Then kraft paper is carried out impregnation, compression molding, its process is: use sizing agent that the special-purpose kraft paper of veneer sheet is flooded, dipping glue amount 0.011 g/cm
2, after dipping, kraft paper is placed in 120 ℃ of baking oven Procuring and obtained prepreg in 15 minutes, then carries out pressing plate: prepreg is placed on the thermocompressor of 110 ℃ press curing 60min under 50MPa, obtains paper-based laminate.
According to " Test methods of evaluating the properties of woodbased panels and surface decorated woodbased panels " GB/T 17657-1999, plate is placed in boiling water and boils 2h, obtain test result: plate surfacing, without bubbling, without layering, rate of body weight gain 16.16% thickens rate 10.94%.
Embodiment 3:
Add 2.8kg(6.5mol in the reaction unit that thermometer, reflux condensation mode and whipping appts are housed) the TGIC by product, be heated to 90 ℃ and under agitation add 130.6g(2.2mol) urea, react 2h under 90 ℃.Reaction obtains faint yellow transparent products after finishing, and the solid content of product is 50.42%, and viscosity is 17mPas.With product solid content modulation 42%, with solid content be that 45% urea-formaldehyde resin is by 1 ︰ 2(mass ratio) mix and obtain sizing agent.
Then kraft paper is carried out impregnation, compression molding, its process is: use sizing agent that the special-purpose kraft paper of veneer sheet is flooded, dipping glue amount 0.009g/cm
2, after dipping, kraft paper is placed in 125 ℃ of baking oven Procuring and obtained prepreg in 12 minutes, then carries out pressing plate: prepreg is placed on the thermocompressor of 150 ℃ press curing 40min under 30MPa, obtains paper-based laminate.
According to " Test methods of evaluating the properties of woodbased panels and surface decorated woodbased panels " GB/T 17657-1999, plate is placed in boiling water and boils 2h, obtain test result: plate surfacing, without bubbling, without layering, rate of body weight gain 13.41% thickens rate 9.73%.
Embodiment 4:
Add 5.2kg(10.2mol in the reaction unit that thermometer, reflux condensation mode and whipping appts are housed) the TGIC by product, be heated to 95 ℃ and under agitation add 130.6g(2.2mol) urea, react 4h under 95 ℃.Reaction obtains faint yellow transparent products after finishing, and the solid content of product is 51.82%, and viscosity is 23mPas.With product solid content modulation 30%, with solid content be that 42% urea-formaldehyde resin is by 2 ︰ 3(mass ratioes) mix and obtain sizing agent.
Then kraft paper is carried out impregnation, compression molding, its process is: use sizing agent that the special-purpose kraft paper of veneer sheet is flooded, dipping glue amount 0.008 g/cm
2, after dipping, kraft paper is placed in 120 ℃ of baking oven Procuring and obtained prepreg in 14 minutes, then carries out pressing plate: prepreg is placed on the thermocompressor of 120 ℃ press curing 50min under 20MPa, obtains paper-based laminate.
According to " Test methods of evaluating the properties of woodbased panels and surface decorated woodbased panels " GB/T 17657-1999, plate is placed in boiling water and boils 2h, obtain test result: plate surfacing, without bubbling, without layering, rate of body weight gain 11.28% thickens rate 10.87%.
Embodiment 5
Add 4.4kg(9.4mol in the reaction unit that thermometer, reflux condensation mode and whipping appts are housed) the TGIC by product, be heated to 90 ℃ and under agitation add 130.6g(2.2mol) urea, react 3h under 90 ℃.Reaction obtains faint yellow transparent products after finishing, and the solid content of product is 50.63%, and viscosity is 18.5mPas.With product solid content modulation 35%, with solid content be that 40% urea-formaldehyde resin is by 3 ︰ 7(mass ratioes) mix and obtain sizing agent.
Then kraft paper is carried out impregnation, compression molding, its process is: use sizing agent that the special-purpose kraft paper of veneer sheet is flooded, dipping glue amount 0.01 g/cm
2, after dipping, kraft paper is placed in 120 ℃ of baking oven Procuring and obtained prepreg in 12 minutes, then carries out pressing plate: prepreg is placed on the thermocompressor of 160 ℃ press curing 40min under 30MPa, obtains paper-based laminate.
According to " Test methods of evaluating the properties of woodbased panels and surface decorated woodbased panels " GB/T 17657-1999, plate is placed in boiling water and boils 2h, obtain test result: the plate surface slightly bubbling, without layering, rate of body weight gain 10.41% thickens rate 8.91%.
In above each embodiment, the mole number of described TGIC by product is and is converted into solid content is mole number after 100%.
Comparative Examples 1
Directly with urea-formaldehyde resin, kraft paper is carried out impregnation, the sheet material that compression molding obtains, test result is as shown in table 2; Its test result of sheet material of utilizing the present invention to obtain is as shown in table 1.
Table 1
Table 2
Claims (6)
1. the treatment process of a TGIC by product, is characterized in that, described by product has following chemical structural formula:
Carry out according to following steps:
1) TGIC by product and urea are added in reaction vessel, in 75 ℃ ~ 95 ℃ reflux condensation mode reaction 2 ~ 4h;
2) product that obtains is adjusted to 30% ~ 45% with solid content, with urea-formaldehyde resin by 1 ︰ 4～2 ︰ 3(mass ratioes) mix and obtain sizing agent.
2. the treatment process of a kind of TGIC by product according to claim 1, is characterized in that, wherein 1) in step: the solid content of described TGIC by product is 50% ~ 60%, and the oxirane value scope is 0.4 ~ 0.6;
The TGIC by product is scaled the rear Fu Chan of TGIC of solid content 100% Wu ︰ urea (mol ratio)=2 ︰ 1～5 ︰ 1.
3. the treatment process of a kind of TGIC by product according to claim 2, is characterized in that, wherein 2) solid content of the urea-formaldehyde resin described in step is 40%-45%.
4. a sizing agent that obtains as claimed in claim 1 utilizes method, it is characterized in that, use above-mentioned sizing agent that the special-purpose kraft paper of veneer sheet is flooded, after dipping, kraft paper is placed in 120 ℃～130 ℃ baking oven Procuring and obtained prepreg in 10～15 minutes, then carry out pressing plate: prepreg is placed on the thermocompressor of 110 ℃ ~ 180 ℃ press curing 10min ~ 60min under 10 ~ 50MPa, obtains paper-based laminate.
Viscose agent according to claim 4 utilize method, it is characterized in that, described dipping glue amount is controlled at 0.008 g/cm
2～0.011 g/cm
2
Viscose agent according to claim 4 utilize method, it is characterized in that described pressing plate process: first with press and mould in 100 ℃ of preheating 2min, afterwards several prepregs are put into mould, compression moulding under the pressure of setting, temperature and time.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201310252713 CN103382376A (en) | 2013-06-24 | 2013-06-24 | Treatment method of TGIC by-product and utilization method for obtaining adhesion agent by utilizing same |
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| CN 201310252713 CN103382376A (en) | 2013-06-24 | 2013-06-24 | Treatment method of TGIC by-product and utilization method for obtaining adhesion agent by utilizing same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104762040A (en) * | 2015-03-26 | 2015-07-08 | 北京林业大学 | Low-toxicity urea resin adhesive and preparation method thereof |
| CN110204702A (en) * | 2019-07-08 | 2019-09-06 | 黄山华惠科技有限公司 | A kind of hydroxy polyester resin and preparation method based on the preparation of TGIC byproduct |
| CN112358589A (en) * | 2020-12-02 | 2021-02-12 | 恩宜瑞(江苏)环境发展有限公司 | Method for preparing high-bonding-strength phenolic resin by resource utilization of dai seek byproduct |
-
2013
- 2013-06-24 CN CN 201310252713 patent/CN103382376A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104762040A (en) * | 2015-03-26 | 2015-07-08 | 北京林业大学 | Low-toxicity urea resin adhesive and preparation method thereof |
| CN110204702A (en) * | 2019-07-08 | 2019-09-06 | 黄山华惠科技有限公司 | A kind of hydroxy polyester resin and preparation method based on the preparation of TGIC byproduct |
| CN110204702B (en) * | 2019-07-08 | 2021-03-26 | 黄山华惠科技有限公司 | Hydroxyl polyester resin prepared based on TGIC byproduct and preparation method thereof |
| CN112358589A (en) * | 2020-12-02 | 2021-02-12 | 恩宜瑞(江苏)环境发展有限公司 | Method for preparing high-bonding-strength phenolic resin by resource utilization of dai seek byproduct |
| CN112358589B (en) * | 2020-12-02 | 2022-03-01 | 恩宜瑞(江苏)环境发展有限公司 | Method for preparing high-bonding-strength phenolic resin by resource utilization of dai seek byproduct |
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Application publication date: 20131106 |