CN111607045A - Soybean protein-glycidyl methacrylate copolymer and preparation method and application thereof - Google Patents
Soybean protein-glycidyl methacrylate copolymer and preparation method and application thereof Download PDFInfo
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- CN111607045A CN111607045A CN202010635259.9A CN202010635259A CN111607045A CN 111607045 A CN111607045 A CN 111607045A CN 202010635259 A CN202010635259 A CN 202010635259A CN 111607045 A CN111607045 A CN 111607045A
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- glycidyl methacrylate
- soybean protein
- soy protein
- methacrylate copolymer
- copolymer
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 57
- 235000010469 Glycine max Nutrition 0.000 title claims abstract description 40
- 244000068988 Glycine max Species 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 108010073771 Soybean Proteins Proteins 0.000 claims abstract description 62
- 235000019710 soybean protein Nutrition 0.000 claims abstract description 46
- 239000000853 adhesive Substances 0.000 claims abstract description 25
- 230000001070 adhesive effect Effects 0.000 claims abstract description 25
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 229910052757 nitrogen Inorganic materials 0.000 claims description 46
- 239000003999 initiator Substances 0.000 claims description 45
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 29
- 239000003960 organic solvent Substances 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 22
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 18
- 239000003446 ligand Substances 0.000 claims description 17
- 229940001941 soy protein Drugs 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- 238000006467 substitution reaction Methods 0.000 claims description 15
- 238000012644 addition polymerization Methods 0.000 claims description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 10
- 229940071440 soy protein isolate Drugs 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical group CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002516 radical scavenger Substances 0.000 claims description 3
- -1 divinyl tetramine Chemical compound 0.000 claims description 2
- BAPCLPLHWVGHGN-UHFFFAOYSA-N ethene 2-methylprop-2-enoic acid Chemical group C=C.C=C.C=C.CC(=C)C(O)=O BAPCLPLHWVGHGN-UHFFFAOYSA-N 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 125000003700 epoxy group Chemical group 0.000 abstract description 5
- 230000035699 permeability Effects 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 238000012360 testing method Methods 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
- 239000011120 plywood Substances 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 4
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000012716 precipitator Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- ULPUHGTUTHTSCS-UHFFFAOYSA-N n'-[2-[2-aminoethyl(methyl)amino]ethyl]ethane-1,2-diamine Chemical compound NCCN(C)CCNCCN ULPUHGTUTHTSCS-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- 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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of soybean protein adhesives, in particular to a soybean protein-glycidyl methacrylate copolymer and a preparation method and application thereof. The soybean protein-glycidyl methacrylate copolymer provided by the invention has a structure shown in formula I, the main chain is soybean protein, the side chain is a brush copolymer with an epoxy group, the epoxy group-containing glycidyl methacrylate is grafted on the surface of isolated soybean protein, and the epoxy group-containing glycidyl methacrylate are more tightly combined through a covalent bond, so that the compatibility of the grafted copolymer and a soybean protein system is improved, and the water-resistant bonding strength of the copolymer is improved. According to the invention, by controlling the molecular weight of the copolymer, the viscosity of the copolymer is moderate, the coating performance and the permeability of the soybean protein adhesive are improved, and the operability of the soybean protein adhesive is ensured.
Description
Technical Field
The invention relates to the technical field of soybean protein adhesives, in particular to a soybean protein-glycidyl methacrylate copolymer and a preparation method and application thereof.
Background
A substance capable of connecting two or more workpieces or materials together through the actions of adhesion, cohesion and the like of an interface is generally called as an adhesive, and the traditional adhesive mainly comprises a formaldehyde-based adhesive and a petroleum-based adhesive. The formaldehyde-based adhesive can release free formaldehyde and free phenol which are harmful to human bodies during manufacturing, transportation and use, so that the problem of environmental pollution is caused; petroleum-based adhesives belong to non-biodegradable materials, and are difficult to degrade and accumulate in the form of waste after long-term use in a large amount, so that the environment is deteriorated.
The soybean protein adhesive overcomes the defect that formaldehyde-based adhesives can contain harmful substances such as free aldehyde and free phenol in the production, transportation and use processes, is environment-friendly and is more and more concerned by researchers. However, the soybean protein adhesive has the defects of high viscosity and poor water-resistant bonding strength, so that the common chemical method for modifying the soybean protein improves the comprehensive performance. At present, most of modified soy protein adhesives mainly aim at the defects of poor water resistance, low bonding strength and the like, and few researches are made on the viscosity of the soy protein adhesives.
Disclosure of Invention
The invention aims to provide a soybean protein-glycidyl methacrylate copolymer and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a soybean protein-glycidyl methacrylate copolymer, which has a structure shown in a formula I:
wherein, SPI is soybean protein isolate, n is polymerization degree of copolymer grafting monomer, and n is an integer more than or equal to 1.
Preferably, the molecular weight of the soybean protein-glycidyl methacrylate copolymer is 5000-80000 g/mol, and the polydispersity index is 1-2.
The invention provides a preparation method of the soybean protein-glycidyl methacrylate copolymer, which comprises the following steps:
mixing the soy protein isolate, an acid-binding agent, a first organic solvent and an initiator, and carrying out substitution grafting reaction to obtain a soy protein-based initiator;
under the condition of protective atmosphere, mixing the soybean protein-based initiator, a second organic solvent, a ligand, glycidyl methacrylate and a metal catalyst, and carrying out addition polymerization reaction to obtain the soybean protein-glycidyl methacrylate copolymer shown in the formula I.
Preferably, the mass ratio of the soybean protein isolate, the acid-binding agent, the first organic solvent and the initiator is 5-50: 22-100: 100-500: 0.23-0.8.
Preferably, the acid-binding agent is triethylamine or 4-dimethylaminopyridine; the first organic solvent is at least one of tetrahydrofuran, N-dimethylformamide, dimethylacetamide and trifluoroacetic acid; the initiator is 2-bromo isobutyryl bromide or alpha-bromo ester.
Preferably, the substitution grafting reaction is carried out at room temperature, and the time of the substitution grafting reaction is 24-72 h.
Preferably, the mass ratio of the soybean protein-based initiator to the second organic solvent to the ligand to the glycidyl methacrylate to the metal catalyst is 0.16-0.5: 1-5: 0.001-0.02: 1.6-6: 0.0016-0.05.
Preferably, the second organic solvent is at least one of tetrahydrofuran, N-dimethylformamide, dimethylacetamide and trifluoroacetic acid; the ligand is at least one of N, N, N ', N ' -tetramethylethylenediamine, N, N, N ', N ', N ' -pentamethyl methacrylate divinyl triamine, N, N, N ', N ', N ' -N-butyl hexamethylacrylate divinyl tetramine, 2' -bipyridine, N, N, N ', N ', N ' -pentamethyl divinyl triamine and N, N, N ', N ', N ' -methyl hexamethyl methacrylate triethylene tetramine; the metal catalyst is a copper catalyst.
Preferably, the temperature of the addition polymerization reaction is 60-90 ℃; the time of the addition polymerization reaction is 6-9 h.
The invention provides an application of the soybean protein-glycidyl methacrylate copolymer or the soybean protein-glycidyl methacrylate copolymer prepared by the preparation method in the technical scheme as an adhesive.
The invention provides a soybean protein-glycidyl methacrylate copolymer which has a structure shown in a formula I. The soybean protein-glycidyl methacrylate copolymer provided by the invention has a main chain of soybean protein and a side chain of a brush copolymer with an epoxy group, and a branched chain repeating unit of the brush copolymer at least contains one
The structure is that rather than forming a binary glue (soy protein and curing agent) which is blended by taking hydrogen bonds as main bonding bonds, glycidyl methacrylate containing epoxy groups is grafted on the surface of the soy protein isolate, and the glycidyl methacrylate and the soy protein isolate are more tightly combined through stronger valence bond acting force (covalent bond), so that the compatibility of the graft copolymer and a soy protein system is improved, and the water-resistant bonding strength of the copolymer is improved. Compared with the traditional soy protein adhesive, the soy protein-glycidyl methacrylate copolymer provided by the invention has the advantages that the viscosity and the bonding strength are improved, the viscosity of the copolymer is moderate by controlling the molecular weight of the copolymer, the coating performance and the permeability of the soy protein adhesive are improved, and the operability of the soy protein adhesive is ensured. In addition, compared with solvent type formaldehyde-free glue, the soybean protein-glycidyl methacrylate copolymer provided by the invention does not contain formaldehyde, does not harm human bodies in the production, transportation and use processes, and is more in line with the green development concept.
Detailed Description
The invention provides a soybean protein-glycidyl methacrylate copolymer, which has a structure shown in a formula I:
wherein, SPI is soybean protein isolate, n is polymerization degree of copolymer grafting monomer, and n is an integer more than or equal to 1. In the present invention, n is preferably 35 to 570. According to the invention, by regulating and controlling the polymerization degree, the molecular weight of the copolymer can be controlled to be 5000-80000 g/mol, the polydispersity coefficient is 1-2, the viscosity of the copolymer is moderate, the coating performance and the permeability of the soybean protein adhesive are improved, and the operability of the soybean protein adhesive is ensured. In the invention, the soybean protein isolate is tightly connected with the functional monomer (glycidyl methacrylate) through a covalent bond, so that the water-resistant bonding strength of the soybean protein adhesive can be improved.
The invention provides a preparation method of the soybean protein-glycidyl methacrylate copolymer, which comprises the following steps:
mixing the soy protein isolate, an acid-binding agent, a first organic solvent and an initiator, and carrying out substitution grafting reaction to obtain a soy protein-based initiator;
under the condition of protective atmosphere, mixing the soybean protein-based initiator, a second organic solvent, a ligand, glycidyl methacrylate and a metal catalyst, and carrying out addition polymerization reaction to obtain the soybean protein-glycidyl methacrylate copolymer shown in the formula I.
In the present invention, unless otherwise specified, the starting materials for the preparation used in the present invention are all commercially available products well known in the art.
The soybean protein isolate, the acid-binding agent, the first organic solvent and the initiator are mixed for substitution grafting reaction to obtain the soybean protein-based initiator. In the invention, the mass ratio of the soybean protein isolate, the acid-binding agent, the first organic solvent and the initiator is preferably 5-50: 22-100: 100-500: 0.23-0.8, and more preferably 5-10: 22-23: 200-210: 0.24-0.25. The invention can effectively regulate and control the reaction degree by regulating the dosage of the soybean protein isolate and the initiator, thereby controlling the molecular weight of the copolymer. In the invention, when the molar ratio of the isolated soy protein to the initiator is 1: 0.0046-0.08, the molecular weight of the obtained soy protein-glycidyl methacrylate copolymer is 5000-50000 g/mol, the polydispersity is 1-2, and the viscosity is moderate.
In the present invention, the soy protein isolate is a mixture having a protein content of 90% or more, SPI represents the soy protein isolate, amino and carboxyl groups are characteristic groups of the protein, and the structural formula of the soy protein isolate is represented by:
in the present invention, the acid scavenger is preferably triethylamine or 4-dimethylaminopyridine. In the invention, the acid-binding agent can accelerate the substitution grafting reaction rate and can react with a byproduct HBr, so that the reaction is more complete.
In the present invention, the first organic solvent is preferably at least one of tetrahydrofuran, N-dimethylformamide, dimethylacetamide and trifluoroacetic acid, and more preferably anhydrous tetrahydrofuran.
In the present invention, the initiator is preferably 2-bromoisobutyryl bromide or α -bromo ester. The invention adopts the initiator, one bromine atom in the initiator is used for replacing the grafting reaction, and one bromine atom is left as an initiation active center to initiate Atom Transfer Radical Polymerization (ATRP).
In the present invention, the method for mixing the soy protein isolate, the acid scavenger, the first organic solvent and the initiator is specifically and preferably: dissolving the isolated soy protein and the acid-binding agent in a first organic solvent, then placing the obtained solution in an ice-water bath, adding the initiator, then taking out the system from the ice-water bath, and stirring for reaction at room temperature. The effect of adding the initiator under the ice-water bath condition is to prevent the volatilization of the initiator caused by overhigh temperature.
In the invention, the substitution grafting reaction is preferably carried out at room temperature, and the time of the substitution grafting reaction is preferably 24-72 h, and more preferably 24-48 h. In the present invention, the substitution grafting reaction is preferably performed under stirring conditions, and the reaction efficiency is improved by stirring.
In a specific embodiment of the present invention, when the initiator is 2-bromoisobutyryl bromide, the reaction formula of the substitution grafting reaction is as follows, and the obtained soy protein-based initiator is a macroinitiator with one end capped with a bromine atom:
preferably, after the substitution grafting reaction, the obtained system is dropped into distilled water, vacuum filtration is carried out, the obtained solid matter is repeatedly washed for 3-5 times by using distilled water, and vacuum drying is carried out at 30-60 ℃ until the weight is constant, so that the soybean protein-based initiator is obtained. The system obtained by the substitution grafting reaction is dripped into distilled water to remove the hydrogen bromide as a reaction by-product, thereby being beneficial to the precipitation of the macroinitiator.
In the invention, the initiation point content of the soybean protein-based initiator is preferably 2.6-4.2 mmol/g.
After the soybean protein-based initiator is obtained, the soybean protein-based initiator, a second organic solvent, a ligand, glycidyl methacrylate and a metal catalyst are mixed under the protective atmosphere condition for addition polymerization reaction to obtain the soybean protein-glycidyl methacrylate copolymer shown in the formula I.
In the invention, the mass ratio of the soybean protein-based initiator, the second organic solvent, the ligand, the glycidyl methacrylate and the metal catalyst is preferably 0.16-0.5: 1-5: 0.001-0.02: 1.6-6: 0.0016-0.05, and more preferably 0.164:1:0.001:1.8: 0.002.
In the present invention, the second organic solvent is preferably at least one of tetrahydrofuran, N-dimethylformamide, dimethylacetamide and trifluoroacetic acid, more preferably a mixture of tetrahydrofuran and N, N-dimethylformamide, and when the second organic solvent is a mixture of tetrahydrofuran and N, N-dimethylformamide, the mass ratio of tetrahydrofuran and N, N-dimethylformamide is preferably 9: 1.
In the present invention, the ligand is preferably at least one of N, N '-tetramethylethylenediamine, N', N ″ -pentamethylmethacrylate divinyltriamine, N ', N ″ -N-butylhexamethylacrylate trivinyltetramine, 2' -bipyridine, N ', N ″ -pentamethyldiethylenetriamine, and N, N', N ″ -methyltriethylenetetramine hexamethylacrylate. In the present invention, the ligand can increase the solubility of the metal catalyst, and the complex of the ligand and the metal catalyst remains sufficiently stable to enable the metal catalyst to achieve a suitable atom transfer activity.
In the present invention, the metal catalyst is preferably a copper catalyst, and more preferably at least one of cuprous bromide, cuprous chloride and cupric bromide. The catalyst has higher activity, and the polymerization reaction is faster while the controllability of the addition polymerization reaction is kept.
In the present invention, the method of forming the protective atmosphere preferably comprises evacuating the system and then introducing nitrogen.
In the present invention, the specific method of mixing the soy protein-based initiator, the second organic solvent, the ligand, glycidyl methacrylate, and the metal catalyst is preferably: dissolving a soybean protein-based initiator in a second organic solvent, then adding a ligand and glycidyl methacrylate, sequentially freezing, vacuumizing and charging nitrogen into the obtained system, then adding a metal catalyst, and sequentially freezing, vacuumizing and charging nitrogen. According to the invention, before the metal catalyst is added, the system is preferably subjected to freezing-vacuumizing-nitrogen filling circulation, and the circulation frequency is preferably three times. The invention carries out freezing-vacuumizing-nitrogen charging on the system before adding the metal catalyst, and the effect is to remove oxygen in the system and prevent the metal catalyst from being oxidized by the oxygen.
In the invention, the temperature of the addition polymerization reaction is preferably 60-90 ℃, and more preferably 70-80 ℃; the time of the addition polymerization reaction is preferably 6-9 hours, and more preferably 7-8 hours. In the present invention, the addition polymerization reaction is preferably carried out in an oil bath.
In a specific embodiment of the present invention, the reaction formula of the addition polymerization reaction is:
the present invention preferably further comprises, after the addition polymerization reaction: removing the metal catalyst in the system, precipitating the obtained system in methanol, and drying to obtain the soybean protein-glycidyl methacrylate copolymer shown in the formula I. In the present invention, the method of removing the metal catalyst is preferably removing the metal catalyst through an alumina column. In the invention, the methanol is preferably cold methanol, and the temperature of the methanol is preferably-4-0 ℃. The invention uses cold methanol as a precipitator to separate out precipitates from a reaction system in which the metal catalyst is removed. The invention preferably dries the obtained precipitate to obtain the soybean protein-glycidyl methacrylate copolymer shown in the formula I. In the invention, the drying temperature is preferably 50-60 ℃, and the drying time is preferably 2-3 h.
The invention takes environment-friendly natural macromolecules (soybean protein isolate) as raw materials, utilizes Atom Transfer Radical Polymerization (ATRP) to graft and modify the soybean protein, has high and controllable reaction process, and can generate the copolymer with controllable molecular weight, uniform distribution and controllable grafting density.
The invention also provides an application of the soybean protein-glycidyl methacrylate copolymer prepared by the technical scheme or the soybean protein-glycidyl methacrylate copolymer prepared by the preparation method of the technical scheme as an adhesive, and the soybean protein-glycidyl methacrylate copolymer is particularly applied to the fields of wood processing, packaging, transportation, building and papermaking. The soybean protein-glycidyl methacrylate copolymer provided by the invention has the advantages of controllable viscosity, high water-resistant bonding strength, safety in use and wide application prospect.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Dissolving 10 parts by weight of soybean protein isolate powder and 22.62 parts by weight of 4-Dimethylaminopyridine (DMAP) in 200 parts by weight of anhydrous tetrahydrofuran, placing the mixture in an ice-water bath, slowly adding 0.24 part by weight of 2-bromoisobutyryl bromide, and stirring the mixture at room temperature for reaction for 24 hours; after the reaction is finished, dripping the obtained reaction liquid into 500 parts of distilled water, carrying out vacuum filtration, repeatedly washing for 3-5 times by using the distilled water, and carrying out vacuum drying at 50 ℃ to constant weight to obtain a soybean protein-based initiator, wherein the content of initiation points is 4.2 mmol/g;
adding 0.164 part of the soybean protein-based initiator, 0.9 part of anhydrous tetrahydrofuran and 0.1 part of N, N-dimethylformamide into a Sulenk bottle, adding 0.001 part of ligand N, N, N ', N ', N ' -pentamethyl divinyl triamine and 1.8 parts of monomer glycidyl methacrylate after the soybean protein-based initiator is completely dissolved, adding 0.002 part of cuprous bromide into the Sulenk bottle after three freezing-vacuumizing-nitrogen charging circulation processes, putting the Sulenk bottle into an oil bath at 80 ℃ after one freezing-vacuumizing-nitrogen charging circulation, removing a copper catalyst through a neutral alumina column after reacting for 8 hours, performing multiple precipitation by using cold methanol at 0 ℃ as a precipitator, and drying the obtained precipitate for 3 hours at 55 ℃ to obtain the soybean protein-glycidyl methacrylate copolymer with the structure shown in the formula I, the product has a molecular weight Mn of 74000 g/mol.
Example 2
Dissolving 5 parts of isolated soy protein powder and 22.62 parts of 4-Dimethylaminopyridine (DMAP) in 200 parts of anhydrous tetrahydrofuran in parts by weight, placing the solution in an ice-water bath, slowly adding 0.24 part of 2-bromoisobutyryl bromide, and stirring and reacting for 24 hours at room temperature; after the reaction is finished, dripping the obtained reaction liquid into 500 parts of distilled water, carrying out vacuum filtration, repeatedly washing for 3-5 times by using the distilled water, and carrying out vacuum drying at 50 ℃ to constant weight to obtain a soybean protein-based initiator, wherein the content of initiation points is 2.6 mmol/g;
adding 0.164 part of the soybean protein-based initiator, 0.9 part of anhydrous tetrahydrofuran and 0.1 part of N, N-dimethylformamide into a Sulenk bottle, adding 0.001 part of ligand N, N, N ', N ', N ' -pentamethyl divinyl triamine and 1.8 parts of monomer glycidyl methacrylate after the soybean protein-based initiator is completely dissolved, adding 0.002 part of cuprous bromide into the Sulenk bottle after three freezing-vacuumizing-nitrogen charging circulation processes, putting the Sulenk bottle into an oil bath at 80 ℃ after one freezing-vacuumizing-nitrogen charging circulation, removing a copper catalyst through a neutral alumina column after 8 hours of reaction, performing multiple precipitation by using cold methanol at 0 ℃ as a precipitator, drying the obtained precipitate at 60 ℃ for 2.5 hours to obtain the soybean protein-glycidyl methacrylate copolymer with the structure shown in the formula I, the molecular weight Mn of the product was 66000 g/mol.
Example 3
Dissolving 10 parts by weight of soybean protein isolate powder and 22.62 parts by weight of 4-Dimethylaminopyridine (DMAP) in 200 parts by weight of anhydrous tetrahydrofuran, placing the mixture in an ice-water bath, slowly adding 0.24 part by weight of 2-bromoisobutyryl bromide, and stirring the mixture at room temperature for reaction for 24 hours; after the reaction is finished, dripping the obtained reaction liquid into 500 parts of distilled water, carrying out vacuum filtration, repeatedly washing for 3-5 times by using the distilled water, and carrying out vacuum drying at 50 ℃ to constant weight to obtain a soybean protein-based initiator, wherein the content of initiation points is 4.2 mmol/g;
adding 0.164 part of the soybean protein-based initiator, 0.9 part of anhydrous tetrahydrofuran and 0.1 part of N, N-dimethylformamide into a Sulenk bottle, adding 0.001 part of ligand N, N, N ', N ', N ' -pentamethyl divinyl triamine and 1.8 parts of monomer glycidyl methacrylate after the soybean protein-based initiator is completely dissolved, adding 0.004 part of cuprous bromide into the Sulenk bottle after three freezing-vacuumizing-nitrogen charging circulation processes, putting the Sulenk bottle into an oil bath at 80 ℃ after one freezing-vacuumizing-nitrogen charging circulation, removing a copper catalyst through a neutral alumina column after 8 hours of reaction, performing multiple precipitation by using cold methanol at 0 ℃ as a precipitator, and drying the obtained precipitate for 3 hours at 50 ℃ to obtain the soybean protein-glycidyl methacrylate copolymer with the structure shown in the formula I, the molecular weight Mn of the product was 60000 g/mol.
Bonding Strength test example
1. Manufacture of plywood
Glue mixing: respectively taking 20g of the soybean protein-glycidyl methacrylate copolymer prepared in the examples 1-3, adding 80g of water into a beaker, respectively adding 20g of calcium carbonate, and uniformly stirring by using a glass rod;
determining the coating weight, specifically 200g/m2(single-sided), uniformly coating the prepared glue on two sides of the core plate by using a brush, and then covering plates on two sides of the core plate to obtain a plate blank;
aging the plate blank at room temperature for a period of time, and carrying out cold pressing operation under the condition of 1.0 MPa; releasing pressure and taking the board to prepare a plywood;
2. pretreatment of test specimens
Manufacturing a test piece: plywood test pieces E-1 (corresponding to example 1), E-2 (corresponding to example 2) and E-3 (corresponding to example 3) are manufactured according to the general technical conditions of common plywood in the part 3 of the national GB/T9846-2004 standard;
secondly, testing the bonding strength according to the national GB/T9846-2004 standard, soaking the test piece, and treating the national II-type plywood: soaking the test piece in hot water of 63 +/-3 ℃ for 3h, taking out the test piece, cooling the test piece for 10min at room temperature, and then testing the bonding strength;
adjusting a universal wood experiment machine, and detecting the bonding strength;
3. require that
The longitudinal axis of the test piece is consistent with the axis of a movable chuck of the wood universal testing machine, and the normal vertical clamping position is kept;
secondly, the distance between the clamping part and the saw cut of the test piece is within 5 mm;
thirdly, the loading speed of the test piece is uniform, and the reading of the maximum breaking load is accurate to 5N;
4. results
The calculation formula of the bonding strength of the test piece is shown as formula II,
wherein, P-maximum breaking load (N);
a-actual width (mm) of the specimen sheared off;
b-actual length (mm) of the shear plane of the test piece;
s-bonding strength of test piece (N/mmr);
the results are shown in Table 1.
TABLE 1 bonding Strength test results
As can be seen from Table 1, the bonding strength of the plywood prepared by using the soybean protein-glycidyl methacrylate copolymer provided by the invention as an adhesive is greater than 0.7MPa specified by the national standard, which indicates that the soybean protein-glycidyl methacrylate copolymer provided by the invention has excellent waterproof bonding strength.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A soy protein-glycidyl methacrylate copolymer having the structure of formula I:
wherein, SPI is soybean protein isolate, n is polymerization degree of copolymer grafting monomer, and n is an integer more than or equal to 1.
2. The soy protein-glycidyl methacrylate copolymer according to claim 1, wherein the molecular weight of the soy protein-glycidyl methacrylate copolymer is 5000 to 80000g/mol, and the polydispersity is 1 to 2.
3. A method for preparing the soy protein-glycidyl methacrylate copolymer of claim 1 or 2, comprising the steps of:
mixing the soy protein isolate, an acid-binding agent, a first organic solvent and an initiator, and carrying out substitution grafting reaction to obtain a soy protein-based initiator;
under the condition of protective atmosphere, mixing the soybean protein-based initiator, a second organic solvent, a ligand, glycidyl methacrylate and a metal catalyst, and carrying out addition polymerization reaction to obtain the soybean protein-glycidyl methacrylate copolymer shown in the formula I.
4. The preparation method according to claim 3, wherein the mass ratio of the soy protein isolate, the acid-binding agent, the first organic solvent and the initiator is 5-50: 22-100: 100-500: 0.23-0.8.
5. The method according to claim 3 or 4, wherein the acid scavenger is triethylamine or 4-dimethylaminopyridine; the first organic solvent is at least one of tetrahydrofuran, N-dimethylformamide, dimethylacetamide and trifluoroacetic acid; the initiator is 2-bromo isobutyryl bromide or alpha-bromo ester.
6. The preparation method according to claim 3, wherein the substitution grafting reaction is carried out at room temperature, and the time of the substitution grafting reaction is 24-72 h.
7. The preparation method according to claim 3, wherein the mass ratio of the soy protein-based initiator, the second organic solvent, the ligand, the glycidyl methacrylate and the metal catalyst is 0.16-0.5: 1-5: 0.001-0.02: 1.6-6: 0.0016-0.05.
8. The production method according to claim 3 or 7, characterized in that the second organic solvent is at least one of tetrahydrofuran, N-dimethylformamide, dimethylacetamide, and trifluoroacetic acid; the ligand is at least one of N, N, N ', N ' -tetramethylethylenediamine, N, N, N ', N ', N ' -pentamethyl methacrylate divinyl triamine, N, N, N ', N ', N ' -N-butyl hexamethylacrylate divinyl tetramine, 2' -bipyridine, N, N, N ', N ', N ' -pentamethyl divinyl triamine and N, N, N ', N ', N ' -methyl hexamethyl methacrylate triethylene tetramine; the metal catalyst is a copper catalyst.
9. The method according to claim 3, wherein the temperature of the addition polymerization reaction is 60 to 90 ℃; the time of the addition polymerization reaction is 6-9 h.
10. Use of the soy protein-glycidyl methacrylate copolymer according to claim 1 or 2 or the soy protein-glycidyl methacrylate copolymer prepared by the preparation method according to any one of claims 3 to 9 as an adhesive.
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| JPH0345797A (en) * | 1989-07-06 | 1991-02-27 | Protein Technol Internatl Inc | Improved composition for paper-coating |
| CN101024677A (en) * | 2006-02-21 | 2007-08-29 | 贺宏彬 | Soy-bean protein grafted copolymerized emulsion binder, its preparing method and use |
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