CN103320081B - High-molecular composite adhesive, and preparation method and application thereof - Google Patents
High-molecular composite adhesive, and preparation method and application thereof Download PDFInfo
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- CN103320081B CN103320081B CN201310194019.XA CN201310194019A CN103320081B CN 103320081 B CN103320081 B CN 103320081B CN 201310194019 A CN201310194019 A CN 201310194019A CN 103320081 B CN103320081 B CN 103320081B
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Abstract
The invention relates to a high-molecular composite adhesive, and a preparation method and an application thereof, and belongs to the technical fields of chemical adhesives, resource utilization and composite materials. Plant-based polyester polyol is prepared through adopting agricultural wastes wheat straws, dihydric alcohol, a catalyst and dicarboxylic anhydride. The plant-based polyester polyol and an aqueous solution of konjac glucomannan are blended to prepare a high-molecular composite aqueous emulsion, and the high-molecular composite aqueous emulsion and isocyanate which are individually packaged undergo room-temperature stirring mixing to prepare the high-molecular composite adhesive when used. The adhesive is used for adhering timber.
Description
Technical field
The present invention relates to a kind of polymer composite adhesive and its preparation method and application, belong to chemical sizing agent, resource utilization recycling and technical field of composite materials.
Background technology
At present, the leading sizing agent in based Wood Adhesives industry is urea-formaldehyde resin, resol and terpolycyantoamino-formaldehyde resin.At present, market constantly increases the demand of formaldehyde-free wood sizing agent, and therefore, the green based Wood Adhesives that research and development are prepared taking natural biomass high molecular polymer as raw material, has great importance.
Using natural biomass high molecular polymer to prepare based Wood Adhesives has been reported.As the application number patent that is 201010550481.5, disclose a kind of preparation method of soy protein adhesives, its step is that soybean protein and water are joined in reaction vessel, then add urea successively, Sodium dodecylbenzene sulfonate and 2 mercapto ethanol, under room temperature condition, make soybean protein emulsion; Add glycerol, epoxy resin and solidifying agent six water triethylene diamines, after mixing, at 40～80 DEG C, reaction, prepares water-resisting type soy protein adhesives again.This sizing agent is not containing hazardous and noxious substances such as formaldehyde, phenol, and in use environmental protection, health, can be applicable to based Wood Adhesives.But on the whole, soybean adhesive, its cost is higher, viscosity is too high, poor fluidity, in addition, the intensity of soybean protein and water tolerance have certain lifting by modification, but still have distance compared with petroleum base sizing agent.The based Wood Adhesives environmental protection that utilizes starch to prepare for raw material, but also there is the features such as poor water resistance.
Konjaku is abundant in china natural resources; its main component is konjaku glucomannan (konjac glucomanna); by numerous seminoses and glucose; with β-1; the strong linear polymer coupling together of 4-glucosides, on some glycosyl side chain of its molecule, is connected with the acetyl group of some amount; the molecular ratio of glucose and seminose is 1:1.5-1.7, and molecular weight is up to 10
6dalton, is occurring in nature molecular weight maximum, and has a kind of material of good biological activity, rheologic behavio(u)r.
Summary of the invention
One of technical assignment of the present invention is in order to make up prior art deficiency, and a kind of polymer composite adhesive of preparing taking biomass high molecular polymer as main raw material is provided.
Two of technical assignment of the present invention is to provide the preparation method of this polymer composite adhesive, and this sizing agent has the feature of the high and water-tolerant of bonding action.
Three of technical assignment of the present invention is to provide the application of this polymer composite adhesive, and this sizing agent is for timber gluing, and, water-tolerant high to timber bonding action, resin added are little.
Polymer composite adhesive technical scheme of the present invention is as follows:
1. a polymer composite adhesive
This polymer composite adhesive, be by polymer composite aqueous emulsion and polyphenyl polymethylene polyisocyanates in mass ratio 100:7～10 stirring at room temperature mix and make.
Described polymer composite aqueous emulsion be by oxidized konjac glucomannan water miscible liquid and plant base polyester polyol in mass ratio 100:15～25 blend make;
Described plant base polyester polyol is made by the raw material through chemical reaction of following mass parts:
Dibasic alcohol 100
Rice straw powder 30～40
Catalyzer 2～3
Pyroglutaric acid 20～30
It is one of following that described dibasic alcohol is selected from: ethylene glycol, propylene glycol, butyleneglycol, neopentyl glycol, tirethylene glycol, triethylene Glycol;
Described rice straw powder, its particle diameter is less than 10 orders, and water content massfraction is less than 1%;
It is one of following that described catalyzer is selected from: hydrochloric acid, sulfuric acid, p-methyl benzenesulfonic acid, Phenylsulfonic acid.
2. above-described polymer composite adhesive, preparation process is as follows:
(1) prepare plant base polyester polyol
In the dibasic alcohol of 100 mass parts, under stirring, add rice straw powder 15～20 mass parts, catalyzer 2～3 mass parts below 10 orders, after blend evenly, be heated to 160～180 DEG C, insulation 30min; Add again rice straw powder 15～20 mass parts below 10 orders, continue, at 160～180 DEG C of insulation 60～90min, to make plant base polyvalent alcohol; Add Pyroglutaric acid 20～30 mass parts, at 150 DEG C of insulation 30min; Temperature is risen to 190～210 DEG C, insulation 120～150min; Be cooled to normal temperature, make plant base polyester polyol;
It is one of following that described dibasic alcohol is selected from: ethylene glycol, propylene glycol, butyleneglycol, neopentyl glycol, tirethylene glycol, triethylene Glycol;
Described rice straw powder, its particle diameter is less than 10 orders, and water content massfraction is less than 1%;
It is one of following that described catalyzer is selected from: hydrochloric acid, sulfuric acid, p-methyl benzenesulfonic acid, Phenylsulfonic acid.
(2) prepare polymer composite aqueous emulsion
The Rhizoma amorphophalli powder of 0.5-1g is joined in the water of 100mL to 30-40
oc stirs 20-30min and makes it swelling, is that 5%NaOH aqueous solution tune pH is 8-10 with massfraction, adds the H of massfraction 30%
2o
2solution 0.2-1.0g, 40-50
othe alkaline oxygenated 40-50min of C, adjusting pH with dilute hydrochloric acid is 6.5, cooling discharging, makes oxidized konjac glucomannan water miscible liquid;
The plant base polyester polyol 100:15～25 blend 30min in mass ratio that oxidized konjac glucomannan water miscible liquid and step (1) are made, makes polymer composite aqueous emulsion.
(3) while use, polymer composite aqueous emulsion is mixed in the ratio stirring at room temperature of 100:7～10 with polyphenyl polymethylene polyisocyanates, sub-composite adhesive secures satisfactory grades.
3. the polymer composite adhesive of preparation as above, is applied to the gluing of wood single-plate overlaid wood based panel, and Amount of spread is 200g/m
2.
More than prepare raw materials used Chemical market or the chemical reagents corporation of being all purchased from.
Gluing step is carried out with reference to GB/T 15104-2006 " Decorative veneered woodbased panel ".One veneer test piece one side is coated with to polymer composite adhesive as panel, and Amount of spread is 200g/m
2, dash board becomes sheet material with the vertical lamination of substrate fiber direction, after gluing first with the pressure of the 1.0MPa 20min that colds pressing, then, in thermocompressor with the pressure of 1.0MPa, in 115 DEG C of even pressurization 3min, the sheet material room temperature ageing 24h after compacting.Sheet material after ageing is sawn into test specimen, surveys its surface bonding intensity.Show taking white oak as the test of examination material, surface bonding strength mean value is greater than 1.0 MPa, and veneer substrate interface destructive rate is greater than 95%, proves thus, and polymer composite adhesive of the present invention has good gluing performance.
Compared with prior art, polymer composite adhesive of the present invention, its outstanding feature is:
(1) select Rhizoma amorphophalli glucomannan as preparing one of raw material of sizing agent.As mentioned above, Amorphophallus rivieri glucomannan sugar is occurring in nature molecular weight maximum, and has a kind of material of the characteristics such as good film forming, thickening, blend, sizing.And konjac glucomannan has natural good biological activity, the sizing agent making taking it as raw material can carry out corrosionproof protection to timber effectively.The present invention is by Rhizoma amorphophalli glucomannan oxidative degradation, reduce molecular weight, improve the emulsifying effectiveness to plant base polyester polyol, increase the cohesive strength of sizing agent, widen the Application Areas of biomass high molecular polymers, make to make sizing agent raw materials cost and reduce, because the objectionable impurities such as formaldehydeless discharges, this sizing agent environmental protection.
(3) the present invention has selected rice straw as another raw material of preparing sizing agent.Rice straw is under the condition of dibasic alcohol and catalyzer existence, and heating is liquefied and is depolymerized to low molecular polylol, and polyvalent alcohol reacts with Pyroglutaric acid and generates macromole polyester polyol.This preparation technology has been new application approach and the technological method that reclaimed useless straw Resource Supply, make on the one hand synthetic sizing agent raw materials cost reduce, on the other hand, can save what prepare with part petroleum replacing chemical resource is petroleum base sizing agent, and added value of product increases.Therefore, the Sustainable development of the industrialization of this sizing agent to rice straw recycle and sizing agent industry, has great importance.
(3) select the linking agent of polyphenyl polymethylene polyisocyanates as polymer composite aqueous emulsion.This mixture contains the free isocyanate group of high reactivity (N=C=O), when hot pressing, active group generation crosslinking reaction taking Mierocrystalline cellulose as main component in can active group, moisture and timber rapidly and in polymer composite aqueous emulsion, form the gluing point glueing joint with timber, after solidifying, form high bonding strength and water tolerance.
(4) this prepare raw materials used, easily obtain, cost is low, industrialization economic and social benefit is remarkable.
Embodiment
Must understand the present invention for better, below in conjunction with embodiment, the invention will be further described, but content of the present invention is not only confined to the following examples.
embodiment 1
(1) prepare plant base polyester polyol
In the ethylene glycol of 200g, under stirring, add rice straw powder 30g mass parts, sulfuric acid 4g below 10 orders, after blend evenly, be heated to 180 DEG C, insulation 30min; Add again the rice straw powder 30g below 10 orders, continue, at 160 DEG C of insulation 90min, to make plant base polyvalent alcohol; Add Pyroglutaric acid 40g, at 150 DEG C of insulation 30min; Temperature is risen to 190 DEG C, insulation 150min; Be cooled to normal temperature, make plant base polyester polyol;
It is one of following that described dibasic alcohol is selected from: ethylene glycol, propylene glycol, butyleneglycol, neopentyl glycol, tirethylene glycol, triethylene Glycol;
Described rice straw powder, its particle diameter is less than 10 orders, and water content massfraction is less than 1%;
(2) prepare polymer composite aqueous emulsion
The Rhizoma amorphophalli powder of 1g is joined in the water of 200g to 30
oc stirs 30min and makes it swelling, is that 5%NaOH aqueous solution tune pH is 8 with massfraction, adds the H of massfraction 30%
2o
2solution 0.4g, 40-50
othe alkaline oxygenated 50min of C, adjusting pH with dilute hydrochloric acid is 6.5, cooling discharging, makes oxidized konjac glucomannan water miscible liquid;
The plant base polyester polyol 100:25 blend 30min in mass ratio that oxidized konjac glucomannan water miscible liquid and step (1) are made, makes polymer composite aqueous emulsion;
(3) while use, polymer composite aqueous emulsion is mixed in the ratio stirring at room temperature of 100:10 with polyphenyl polymethylene polyisocyanates, sub-composite adhesive secures satisfactory grades.
embodiment 2
(1) prepare plant base polyester polyol
In the butyleneglycol of 300g, under stirring, add rice straw powder 60g, p-methyl benzenesulfonic acid 9g below 10 orders, after blend evenly, be heated to 170 DEG C, insulation 30min; Add again the rice straw powder 60g below 10 orders, continue, at 170 DEG C of insulation 75min, to make plant base polyvalent alcohol; Add Pyroglutaric acid 75g, at 150 DEG C of insulation 30min; Temperature is risen to 200 DEG C, insulation 135min; Be cooled to normal temperature, make plant base polyester polyol;
It is one of following that described dibasic alcohol is selected from: ethylene glycol, propylene glycol, butyleneglycol, neopentyl glycol, tirethylene glycol, triethylene Glycol;
Described rice straw powder, its particle diameter is less than 10 orders, and water content massfraction is less than 1%;
(2) prepare polymer composite aqueous emulsion
The Rhizoma amorphophalli powder of 2.1g is joined in the water of 300g to 35
oc stirs 25min and makes it swelling, is that 5%NaOH aqueous solution tune pH is 9 with massfraction, adds the H of massfraction 30%
2o
2solution 1.5g, 45
othe alkaline oxygenated 45min of C, adjusting pH with dilute hydrochloric acid is 6.5, cooling discharging, makes oxidized konjac glucomannan water miscible liquid;
The plant base polyester polyol 100:20 blend 30min in mass ratio that oxidized konjac glucomannan water miscible liquid and step (1) are made, makes polymer composite aqueous emulsion;
(3) while use, polymer composite aqueous emulsion is mixed in the ratio stirring at room temperature of 100:8 with polyphenyl polymethylene polyisocyanates, sub-composite adhesive secures satisfactory grades.
embodiment 3
(1) prepare plant base polyester polyol
In the tirethylene glycol of 300g, under stirring, add rice straw powder 51g, Phenylsulfonic acid 7.5g below 10 orders, after blend evenly, be heated to 175 DEG C, insulation 30min; Add again the rice straw powder 51g below 10 orders, continue, at 180 DEG C of insulation 60min, to make plant base polyvalent alcohol; Add Pyroglutaric acid 90g, at 150 DEG C of insulation 30min; Temperature is risen to 210 DEG C, insulation 120min; Be cooled to normal temperature, make plant base polyester polyol;
It is one of following that described dibasic alcohol is selected from: ethylene glycol, propylene glycol, butyleneglycol, neopentyl glycol, tirethylene glycol, triethylene Glycol;
Described rice straw powder, its particle diameter is less than 10 orders, and water content massfraction is less than 1%;
It is one of following that described catalyzer is selected from: hydrochloric acid, sulfuric acid, p-methyl benzenesulfonic acid, Phenylsulfonic acid;
(2) prepare polymer composite aqueous emulsion
The Rhizoma amorphophalli powder of 3g is joined in the water of 300g to 40
oc stirs 20min and makes it swelling, is that 5%NaOH aqueous solution tune pH is 10 with massfraction, adds the H of massfraction 30%
2o
2solution 3.0g, 50
othe alkaline oxygenated 40min of C, adjusting pH with dilute hydrochloric acid is 6.5, cooling discharging, makes oxidized konjac glucomannan water miscible liquid;
The plant base polyester polyol 100:15 blend 30min in mass ratio that oxidized konjac glucomannan water miscible liquid and step (1) are made, makes polymer composite aqueous emulsion;
(3) while use, polymer composite aqueous emulsion is mixed in the ratio stirring at room temperature of 100:7 with polyphenyl polymethylene polyisocyanates, sub-composite adhesive secures satisfactory grades.
embodiment 4
The gluing that the polymer composite adhesive making in embodiment 1, embodiment 2 and embodiment 3 is applied to respectively to wood single-plate overlaid wood based panel, step is as follows:
One veneer test piece one side is coated with to polymer composite adhesive as panel, and Amount of spread is 200g/m
2, dash board becomes test specimen with the vertical lamination of backboard fiber direction and central layer, after gluing first with the pressure of the 1.0MPa 20min that colds pressing.Then, in thermocompressor, with the pressure of 1.0MPa, in 115 DEG C of 3min that evenly pressurize, the sheet material room temperature ageing 24h after compacting.
Sheet material after ageing is sawn into test specimen, surveys its surface bonding intensity.Taking white oak as examination material, its surface bonding strength mean value is greater than 1.0 MPa, and veneer substrate interface destructive rate is greater than 95%, proves thus, and the polymer composite adhesive making all has good gluing performance.
Claims (2)
1. a polymer composite adhesive, is characterized in that, preparation process is as follows:
(1) prepare plant base polyester polyol
In the dibasic alcohol of 100 mass parts, under stirring, add rice straw powder 15～20 mass parts, catalyzer 2～3 mass parts below 10 orders, after blend evenly, be heated to 160～180 DEG C, insulation 30min; Add again rice straw powder 15～20 mass parts below 10 orders, continue, at 160～180 DEG C of insulation 60～90min, to make plant base polyvalent alcohol; Add Pyroglutaric acid 20～30 mass parts, at 150 DEG C of insulation 30min; Temperature is risen to 190～210 DEG C, insulation 120～150min; Be cooled to normal temperature, make plant base polyester polyol;
It is one of following that described dibasic alcohol is selected from: ethylene glycol, propylene glycol, butyleneglycol, neopentyl glycol, tirethylene glycol, triethylene Glycol;
Described rice straw powder, its particle diameter is less than 10 orders, and water content massfraction is less than 1%;
It is one of following that described catalyzer is selected from: hydrochloric acid, sulfuric acid, p-methyl benzenesulfonic acid, Phenylsulfonic acid;
(2) prepare polymer composite aqueous emulsion
The Rhizoma amorphophalli powder of 0.5-1 mass parts is joined in the water of 100 mass parts to 30-40
oc stirs 20-30min and makes it swelling, is that 5%NaOH aqueous solution tune pH is 8-10 with massfraction, adds the H of massfraction 30%
2o
2solution 0.2-1.0 mass parts, 40-50
othe alkaline oxygenated 40-50min of C, adjusting pH with dilute hydrochloric acid is 6.5, cooling discharging, makes oxidized konjac glucomannan water miscible liquid;
The plant base polyester polyol 100:15～25 blend 30min in mass ratio that oxidized konjac glucomannan water miscible liquid and step (1) are made, makes polymer composite aqueous emulsion;
(3) while use, polymer composite aqueous emulsion is mixed in the ratio stirring at room temperature of 100:7～10 with polyphenyl polymethylene polyisocyanates, sub-composite adhesive secures satisfactory grades.
2. polymer composite adhesive as claimed in claim 1, is characterized in that, is applied to the gluing of wood single-plate overlaid wood based panel, and Amount of spread is 200g/m
2.
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| CN105176490B (en) * | 2015-10-26 | 2017-08-25 | 曹华 | A kind of Wood Adhesive composition |
| CN107400494A (en) * | 2016-05-19 | 2017-11-28 | 长沙市汇华胶粘剂科技有限公司 | A kind of wheat stalk-konjaku flour composite adhesive and preparation method thereof |
| CN107361351A (en) * | 2017-07-21 | 2017-11-21 | 福建农林大学 | A kind of konjaku glucomannan composite emulsifier and preparation method thereof |
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| US3944428A (en) * | 1975-03-06 | 1976-03-16 | National Starch And Chemical Corporation | Alkaline curing corrugating adhesive |
| CN100389164C (en) * | 2006-07-12 | 2008-05-21 | 山东恒冠化工科技有限公司 | Waterproof sealing agent for wires, cables and terminals and its prepn |
| CN101525416A (en) * | 2008-03-04 | 2009-09-09 | 东丽纤维研究所（中国）有限公司 | Biobased polyethylene terephthalate |
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Application publication date: 20130925 Assignee: HEBEI HUATENG WANFUDA FINE CHEMICAL Co.,Ltd. Assignor: University of Jinan Contract record no.: 2015990000614 Denomination of invention: High-molecular composite adhesive, and preparation method and application thereof Granted publication date: 20140910 License type: Exclusive License Record date: 20150715 |
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