CN103435755B - A kind of adhesive preparation method of straw making sheet - Google Patents
A kind of adhesive preparation method of straw making sheet Download PDFInfo
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- CN103435755B CN103435755B CN201310374158.0A CN201310374158A CN103435755B CN 103435755 B CN103435755 B CN 103435755B CN 201310374158 A CN201310374158 A CN 201310374158A CN 103435755 B CN103435755 B CN 103435755B
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Abstract
The invention belongs to technical field of adhesive preparation, relate to a kind of adhesive preparation method that can be used for the making sheet of farm crop straw, comprise and diphenylmethanediisocyanate and polyether glycol NJ-330 are dissolved in acetone, take dibutyl tin dilaurate as catalyzer, add hydroxy propyl methacrylate and carry out end-blocking, then add fluorinated acrylate monomer and be that initiator for reaction is prepared from Diisopropyl azodicarboxylate.According to tackiness agent prepared by the method for the invention, not containing free formaldehyde monomer; And fluorine element is introduced in isocyanate glue system, because of the polarizability that fluorine atom is lower, strong electronegativity, less van der Waals radius, can be combined the C-F key forming high bond energy with carbon atom, the surface energy of the essential groups-CF3 of fluorine carbon compound is extremely low, make tackiness agent good stability, there is after film forming good water tolerance and mechanical mechanics property, and between surface-treated stalk, there is stronger bonding effect, by usual regenerated fiber board production technology, make artificial straw plate.
Description
Technical field
The invention belongs to technical field of adhesive preparation, relate to the preparation of tackiness agent, particularly relate to a kind of adhesive preparation method that can be used for the making sheet of farm crop straw.
Technical background
Wheat straw, as the byproduct of agriculture production, is used to make cob plate the earliest, is used for building house.Germany in 1905 once to mix with tackiness agent with agricultural crop straw raw materials such as wheat straws and carried out making sheet research; 1930 ~ 1940 years U.S. also carried out utilizing this type of raw material to manufacture the research of insulcrete.Britain started to manufacture straw board with straw and wheat straw in the mid-40 in 20th century, and this technology once transferred the possession of country of twenties, the world.Within 1970, UNIDO has held the symposial having 13 country's participation with regard to non-wood based panel, and Wood-based Panel Production utilizes agricultural wastes to be extended to various stalk material.But really researching and developing with wheat straw is raw material, produce wood-based plate and large-scale application in production and life in, still just developed rapidly in recent years.
The people such as the J.Hague in British Wales university Biocomposite material research centre adopt urea-formaldehyde resin adhesive respectively, Phenol aldehyde resin and isocyanate glue, the particleboard production of the agricultural wastes manufactures such as wheat straw is conducted in-depth research, result shows: if manufacture sheet material with these residuums by the method for wood planing card, its low strength, this is mainly because the wax on their surfaces and silicrete affect the glue performance of tackiness agent, therefore effects on surface is answered to carry out pre-treatment and improve manufacturing process, simultaneously, be also noted that the selection of shaving shape, internal bond strength is improved with this.
Famous Bayer company of Germany and former Bison company research centre also produce this field of shaving board to yearly plant as raw material and explore.Result of study shows: although carry out oxygenation pretreatment to wheat straw material, conventional urea-formaldehyde adhesive can be used to manufacture wheat straw board, and technique is not easily implemented, and cost is higher, is unfavorable for generally adopting and promoting; When using polymeric isocyanate glue (PMDI), the better performances of wheat straw board, applies inner pattern releasing agent applicable and can solve haftplatte problem, and technique is easily implemented; Meanwhile, research also show, if 100% manufactures wood-based plate with wheat straw as raw material, resin added compare with timber more greatly, be generally 3%-5%, and timber is 2.5%-3%, this makes the cost of glue increase to some extent.
Yangzhou University's journal (natural science edition), 2002,5 (4): 80-82, with discarded stalk and resol for main raw material, carbonization → ball milling mixing → pressure forming → sintering through stalk waits technical process to prepare composite eco material, the density of this material is suitable with wood ceramics with conductivity, can be used as the sheet materials such as magnetron sputtering carbon back target and brush.But the tackiness agent used in this technique is resol, containing free formaldehyde, there is certain damaging effect to HUMAN HEALTH.
Forest product industry, 2001,28 (5): 36-38,42, take MDI as production of adhesive Properties of Wheat-straw Particleboard, and determine rational MDI applied amount by test.Compared with conventional tackiness agent, MDI tackiness agent has that clamping time is short, glue-line is water-fast and the advantage such as ageing-resistant performance is good, and weak point is that cost is high, and haftplatte easily occurs during MDI adhesive producing shaving board, toxic, and require that metering and pumping system can not be polluted by water.
Summary of the invention
For overcoming the shortcoming that aforesaid method exists, the invention discloses a kind of adhesive preparation method that can be used for the making sheet of farm crop straw.
A kind of adhesive preparation method of straw making sheet, comprise and diphenylmethanediisocyanate (MDI) and polyether glycol NJ-330 are dissolved in acetone, with dibutyl tin dilaurate (T-12) for catalyzer, add hydroxy propyl methacrylate (HPMA) and carry out end-blocking, then fluorinated acrylate monomer is added and with Diisopropyl azodicarboxylate (AIBN) for initiator, concrete steps are as follows:
A, diphenylmethanediisocyanate (MDI) and polyether glycol NJ-330 dissolved in acetone, be heated to 65 DEG C, the consumption of wherein said NJ-330 is 50 ~ 300% of MDI quality, preferably 150%; The consumption of described acetone is 50 ~ 350% of MDI quality, preferably 150%;
B, in system, add dibutyl tin dilaurate (T-12) be catalyzer, and its consumption is 0.1% ~ 0.35% of MDI quality, preferably 0.25%, and be warmed up to 90 DEG C and stir 1 ~ 5h, be preferably 3.5h;
C, step B gained system is cooled to 50 DEG C, add hydroxy propyl methacrylate (HPMA) and carry out end-blocking, its consumption is 50 ~ 80% of MDI quality, preferably 60%, after stirring 3h, be cooled to 35 DEG C;
D, add fluorinated acrylate monomer to step C gained system, be warming up to 80 DEG C of reactions, add Diisopropyl azodicarboxylate (AIBN) initiator, reaction 0.5 ~ 4.0h, preferred 3.0h; The consumption of described fluorinated acrylate monomer is 50 ~ 120% of HPMA consumption, preferably 100%; The consumption of described Diisopropyl azodicarboxylate is 0.1 ~ 0.4% of fluorochemical monomer total mass, preferably 0.3%, and the obtained tackiness agent that can be used for straw making sheet.
Fluorinated acrylate monomer of the present invention can be any one in methacrylic acid ten trifluoro monooctyl ester, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate, trifluoroethyl methacrylate, Hexafluorobutyl mathacrylate or vinylformic acid hexafluoro butyl ester, preferable methyl vinylformic acid hexafluoro butyl ester.
According to the tackiness agent that the method for the invention is obtained, water-absorbent after tested after adhesive samples film forming and tensile strength, tackiness agent good stability synthesized by discovery, there is after film forming good water tolerance and mechanical mechanics property, and between surface-treated stalk, there is stronger bonding effect, by usual regenerated fiber board production technology, make artificial straw plate.
The diphenylmethanediisocyanate MDI that the present invention is used, purchased from the broad Chemical Co., Ltd. in Shanghai; Polyether glycol (NJ-330,3000g/mol), purchased from Ningwu Chemical Co., Ltd., Jurong; Hydroxy propyl methacrylate is purchased from Chemical Reagent Co., Ltd., Sinopharm Group; Fluorochemical monomer is purchased from Harbin Xue Jiafu chemistry of silicones company limited; All the other chemical reagent are all purchased from Chemical Reagent Co., Ltd., Sinopharm Group.
Beneficial effect
The special-purpose adhesive of farm crop straw making sheet that prepared by the present invention can be used for, not containing free formaldehyde monomer; And fluorine element is introduced in isocyanate glue system, because of the structural feature of fluorine atom, as: the polarizability that fluorine atom is lower, strong electronegativity, less van der Waals radius
the C-F key (540kJ/mol) forming high bond energy can be combined, the essential groups-CF of fluorine carbon compound with carbon atom
3surface energy only have 6mJ/m
2, be the material that current known surface can be minimum, make synthesized tackiness agent good stability, there is after film forming good water tolerance and mechanical mechanics property.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail, but the present invention is not limited to following examples.
Embodiment 1
Being equipped with agitator, reflux condensing tube, temperature take into account in the 500mL four-hole bottle of feeding device, add diphenylmethanediisocyanate MDI, 10g polyether glycol NJ-330 and the 10g acetone of 20g, abundant stirring makes it dissolve, system is warmed up to 65 DEG C, adds the T-12 catalyzer of 0.02g, system is warmed up to 90 DEG C, 50 DEG C are cooled to after reaction 1h, the hydroxy propyl methacrylate (HPMA) adding 10g carries out end-blocking, after stirring 3h, is cooled to 35 DEG C.In above-mentioned system, add 5g methacrylic acid ten trifluoro monooctyl ester monomer, be warming up to 80 DEG C of reactions, add 0.05g Diisopropyl azodicarboxylate AIBN initiator, reaction 0.5h.Obtain the special-purpose adhesive (MGJNJ-1) that can be used for the making sheet of farm crop straw.
Embodiment 2
Agitator is being housed, reflux condensing tube, temperature is taken into account in the 500mL four-hole bottle of feeding device, add the diphenylmethanediisocyanate MDI of 20g, 20g polyether glycol NJ-330 and 20g acetone, abundant stirring makes it dissolve, system is warmed up to 65 DEG C, add the T-12 catalyzer of 0.03g, system is warmed up to 90 DEG C, 50 DEG C are cooled to after reaction 3h, the hydroxy propyl methacrylate (HPMA) adding 12g carries out end-blocking, after stirring 3h, be cooled to 35 DEG C, 7.5g dodecafluorhe-ptylacrylate monomer is added in above-mentioned system, be warming up to 80 DEG C of reactions, add 0.15g Diisopropyl azodicarboxylate AIBN initiator, reaction 1h.Obtain the special-purpose adhesive (MGJNJ-2) that can be used for the making sheet of farm crop straw.
Embodiment 3
Agitator is being housed, reflux condensing tube, temperature is taken into account in the 500mL four-hole bottle of feeding device, add the diphenylmethanediisocyanate MDI of 20g, 30g polyether glycol NJ-330 and 30g acetone, abundant stirring makes it dissolve, system is warmed up to 65 DEG C, add the T-12 catalyzer of 0.04g, system is warmed up to 90 DEG C, 50 DEG C are cooled to after reaction 2.5h, the hydroxy propyl methacrylate (HPMA) adding 14g carries out end-blocking, after stirring 3h, be cooled to 35 DEG C, 10g dodecafluoroheptyl methacrylate monomer is added in above-mentioned system, be warming up to 80 DEG C of reactions, add 0.02g Diisopropyl azodicarboxylate AIBN initiator, reaction 1.5h.Obtain the special-purpose adhesive (MGJNJ-3) that can be used for the making sheet of farm crop straw.
Embodiment 4
Agitator is being housed, reflux condensing tube, temperature is taken into account in the 500mL four-hole bottle of feeding device, add the diphenylmethanediisocyanate MDI of 20g, 40g polyether glycol NJ-330 and 45g acetone, abundant stirring makes it dissolve, system is warmed up to 65 DEG C, add the T-12 catalyzer of 0.05g, system is warmed up to 90 DEG C, 50 DEG C are cooled to after reaction 1.5h, the hydroxy propyl methacrylate (HPMA) adding 15g carries out end-blocking, after stirring 3h, be cooled to 35 DEG C, 9g trifluoroethyl methacrylate monomer is added in above-mentioned system, be warming up to 80 DEG C of reactions, add 0.015g Diisopropyl azodicarboxylate AIBN initiator, reaction 2h.Obtain the special-purpose adhesive (MGJNJ-4) that can be used for the making sheet of farm crop straw.
Embodiment 5
Agitator is being housed, reflux condensing tube, temperature is taken into account in the 500mL four-hole bottle of feeding device, add the diphenylmethanediisocyanate MDI of 20g, 50g polyether glycol NJ-330 and 50g acetone, abundant stirring makes it dissolve, system is warmed up to 65 DEG C, add the T-12 catalyzer of 0.07g, system is warmed up to 90 DEG C, 50 DEG C are cooled to after reaction 2h, the hydroxy propyl methacrylate (HPMA) adding 13g carries out end-blocking, after stirring 3h, be cooled to 35 DEG C, 12g Hexafluorobutyl mathacrylate monomer is added in above-mentioned system, be warming up to 80 DEG C of reactions, add 0.025g Diisopropyl azodicarboxylate AIBN initiator, reaction 2.5h.Obtain the special-purpose adhesive (MGJNJ-5) that can be used for the making sheet of farm crop straw.
Embodiment 6
Agitator is being housed, reflux condensing tube, temperature is taken into account in the 500mL four-hole bottle of feeding device, add the diphenylmethanediisocyanate MDI of 20g, 60g polyether glycol NJ-330 and 70g acetone, abundant stirring makes it dissolve, system is warmed up to 65 DEG C, add the T-12 catalyzer of 0.06g, system is warmed up to 90 DEG C, 50 DEG C are cooled to after reaction 3h, the hydroxy propyl methacrylate (HPMA) adding 16g carries out end-blocking, after stirring 3h, be cooled to 35 DEG C, 10g vinylformic acid hexafluoro butyl ester monomer is added in above-mentioned system, be warming up to 80 DEG C of reactions, add 0.04g Diisopropyl azodicarboxylate AIBN initiator, reaction 3h.Obtain the special-purpose adhesive (MGJNJ-6) that can be used for the making sheet of farm crop straw.
Embodiment 7
Agitator is being housed, reflux condensing tube, temperature is taken into account in the 500mL four-hole bottle of feeding device, add the diphenylmethanediisocyanate MDI of 20g, 30g polyether glycol NJ-330 and 70g acetone, abundant stirring makes it dissolve, system is warmed up to 65 DEG C, add the T-12 catalyzer of 0.05g, system is warmed up to 90 DEG C, 50 DEG C are cooled to after reaction 3.5h, the hydroxy propyl methacrylate (HPMA) adding 12g carries out end-blocking, after stirring 3h, be cooled to 35 DEG C, 12g Hexafluorobutyl mathacrylate monomer is added in above-mentioned system, be warming up to 80 DEG C of reactions, add 0.036g Diisopropyl azodicarboxylate AIBN initiator, reaction 3h.Obtain the special-purpose adhesive (MGJNJ-7) that can be used for the making sheet of farm crop straw.
Embodiment 8
Agitator is being housed, reflux condensing tube, temperature is taken into account in the 500mL four-hole bottle of feeding device, add the diphenylmethanediisocyanate MDI of 20g, 40g polyether glycol NJ-330 and 60g acetone, abundant stirring makes it dissolve, system is warmed up to 65 DEG C, add the T-12 catalyzer of 0.06g, system is warmed up to 90 DEG C, 50 DEG C are cooled to after reaction 4h, the hydroxy propyl methacrylate (HPMA) adding 12g carries out end-blocking, after stirring 3h, be cooled to 35 DEG C, 10g Hexafluorobutyl mathacrylate monomer is added in above-mentioned system, be warming up to 80 DEG C of reactions, add 0.04g Diisopropyl azodicarboxylate AIBN initiator, reaction 4h.Obtain the special-purpose adhesive (MGJNJ-8) that can be used for the making sheet of farm crop straw.
Experimental technique
Measure the water-absorbent after special-purpose adhesive sample film forming and tensile strength, result is as shown in the table.
Sample | Tensile strength (MPa) | Water-intake rate (%) |
MGJNJ-1 | 4.01 | 12.67 |
MGJNJ-2 | 4.90 | 10.26 |
MGJNJ-3 | 4.98 | 9.98 |
MGJNJ-4 | 5.16 | 10.29 |
MGJNJ-5 | 5.23 | 8.67 |
MGJNJ-6 | 5.47 | 9.40 |
MGJNJ-7 | 6.36 | 7.59 |
MGJNJ-8 | 5.77 | 9.59 |
Result shows, the tackiness agent that the present invention obtains, good stability, there is after film forming good water tolerance and mechanical mechanics property, and between surface-treated straw, there is stronger bonding effect, by usual regenerated fiber board production technology, make artificial straw plate.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every utilize specification sheets of the present invention to do equivalent structure or the conversion of equivalent flow process, or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (8)
1. the adhesive preparation method of a straw making sheet, comprise and diphenylmethanediisocyanate MDI and polyether glycol NJ-330 is dissolved in acetone, with dibutyl tin dilaurate T-12 for catalyzer, add hydroxy propyl methacrylate HPMA and carry out end-blocking, then fluorinated acrylate monomer is added and with Diisopropyl azodicarboxylate AIBN for initiator, it is characterized in that, concrete steps are as follows:
A, diphenylmethanediisocyanate MDI and polyether glycol NJ-330 dissolved in acetone, be heated to 65 DEG C, the consumption of wherein said NJ-330 is 50 ~ 300% of MDI quality, and the consumption of described acetone is 50 ~ 350% of MDI quality;
B, in system, add dibutyl tin dilaurate T-12 be catalyzer, and its consumption is 0.1% ~ 0.35% of MDI quality, is warmed up to 90 DEG C and stirs 1 ~ 5h;
C, step B gained system is cooled to 50 DEG C, add hydroxy propyl methacrylate HPMA and carry out end-blocking, its consumption is 50 ~ 80% of MDI quality, after stirring 3h, is cooled to 35 DEG C;
D, add fluorinated acrylate monomer to step C gained system, be warming up to 80 DEG C of reactions, add Diisopropyl azodicarboxylate AIBN initiator, reaction 0.5 ~ 4.0h; The consumption of described fluorinated acrylate monomer is 50 ~ 120% of HPMA consumption, and the consumption of described Diisopropyl azodicarboxylate is 0.1 ~ 0.4% of fluorochemical monomer total mass, the obtained tackiness agent that can be used for straw making sheet.
2. the adhesive preparation method of straw making sheet according to claim 1, is characterized in that, the consumption of NJ-330 described in steps A is 150% of MDI quality, and the consumption of described acetone is 150% of MDI quality.
3. the adhesive preparation method of straw making sheet according to claim 1, is characterized in that, the consumption of the T-12 of dibutyl tin dilaurate described in step B is 0.25% of MDI quality, is warmed up to 90 DEG C and stirs 3.5h.
4. the adhesive preparation method of straw making sheet according to claim 1, is characterized in that, the consumption of the HPMA of hydroxy propyl methacrylate described in step C is 60% of MDI quality, after stirring 3h, is cooled to 35 DEG C.
5. the adhesive preparation method of straw making sheet according to claim 1, is characterized in that, the AIBN of Diisopropyl azodicarboxylate described in step D initiator, reaction 3.0h; The consumption of described fluorinated acrylate monomer is 100% of HPMA consumption, and the consumption of described Diisopropyl azodicarboxylate is 0.3% of fluorochemical monomer total mass, the obtained tackiness agent that can be used for straw making sheet.
6. the adhesive preparation method of straw making sheet according to claim 1 or 5, it is characterized in that, described fluorinated acrylate monomer can be any one in methacrylic acid ten trifluoro monooctyl ester, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate, trifluoroethyl methacrylate, Hexafluorobutyl mathacrylate or vinylformic acid hexafluoro butyl ester.
7. the adhesive preparation method of straw making sheet according to claim 1 or 5, is characterized in that, described fluorinated acrylate monomer is Hexafluorobutyl mathacrylate.
8. the tackiness agent of the straw making sheet prepared according to aforementioned either method.
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CN101230120A (en) * | 2008-01-10 | 2008-07-30 | 安徽大学 | Radiation polymerization method for aqueous polyurethane-fluorine containing acrylic ester emulsion |
CN102816285A (en) * | 2012-08-14 | 2012-12-12 | 江苏大学 | Aqueous fluorine-containing acrylate modified polyurethane coating, preparation method and application thereof |
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CN101230120A (en) * | 2008-01-10 | 2008-07-30 | 安徽大学 | Radiation polymerization method for aqueous polyurethane-fluorine containing acrylic ester emulsion |
CN102816285A (en) * | 2012-08-14 | 2012-12-12 | 江苏大学 | Aqueous fluorine-containing acrylate modified polyurethane coating, preparation method and application thereof |
Non-Patent Citations (2)
Title |
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Preparation, mechanical properties and surface morphologies of waterborne fluorinated polyurethane-acrylate;Yingying Wang et al;《Progress in Organic Coatings》;20130305;第76卷;第876-883页 * |
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