WO2019119559A1 - 一种高性能醚化生物基树脂及其制备方法 - Google Patents

一种高性能醚化生物基树脂及其制备方法 Download PDF

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WO2019119559A1
WO2019119559A1 PCT/CN2018/072054 CN2018072054W WO2019119559A1 WO 2019119559 A1 WO2019119559 A1 WO 2019119559A1 CN 2018072054 W CN2018072054 W CN 2018072054W WO 2019119559 A1 WO2019119559 A1 WO 2019119559A1
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etherified
bio
reaction
ether
resin
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刘仁
刘敬成
张丽萍
袁研
陈淼
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Jiangnan University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/40—Chemically modified polycondensates
    • C08G12/42—Chemically modified polycondensates by etherifying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/40—Chemically modified polycondensates
    • C08G12/42—Chemically modified polycondensates by etherifying
    • C08G12/421—Chemically modified polycondensates by etherifying of polycondensates based on acyclic or carbocyclic compounds
    • C08G12/422—Chemically modified polycondensates by etherifying of polycondensates based on acyclic or carbocyclic compounds based on urea or thiourea
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/40—Chemically modified polycondensates
    • C08G12/42—Chemically modified polycondensates by etherifying
    • C08G12/424—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds
    • C08G12/425—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds based on triazines
    • C08G12/427—Melamine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/32—Modified amine-aldehyde condensates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/32—Modified amine-aldehyde condensates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09J161/32—Modified amine-aldehyde condensates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • D06M15/427—Amino-aldehyde resins modified by alkoxylated compounds or alkylene oxides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/26—Aminoplasts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the invention relates to a high performance etherified bio-based resin and a preparation method thereof, and belongs to the technical field of synthetic resins.
  • the amino resin refers to a type of thermosetting resin having high crosslinking activity obtained by subjecting an amino group-containing (-NH 2 )-containing compound to methylolation reaction with formaldehyde and then reacting with a lower alcohol to carry out etherification modification.
  • the coating film usually obtained by using an amino resin as a crosslinking agent has the advantages of high hardness, high gloss, good color retention, chemical resistance and weather resistance, and is therefore widely used in the coating industry, leather tanning agents, and adhesives. Agents, flame retardant materials and other fields.
  • the melamine formaldehyde resin contains a large amount of -CH 2 OH and -NH- groups, which is very polar, unstable, and insoluble in organic solvents. Therefore, it is industrially modified by etherification with a lower alcohol, and -CH 2
  • the OH group is etherified, reducing its polarity and improving its solubility. Since the raw material of the synthetic etherified melamine formaldehyde resin contains formaldehyde, a certain amount of methylene is inevitably contained in the product. Methylene groups release formaldehyde when heated at high temperatures.
  • HMMM products will also have a small amount of formaldehyde released in the application.
  • the imino group is very active and unstable, and it is most prone to self-crosslinking reaction, and the storage stability is poor.
  • the industrially produced etherified melamine resin usually contains a certain amount of solvent, and a low degree of etherification also lowers the solid content. It can be seen from the above that the etherified melamine resin has problems such as poor storage stability, high free formaldehyde content, low solid content, and large odor. The long-term exposure to the environment may also cause potential harm to human health, so that it is in the paint, Applications in inks are limited to a certain extent.
  • CN 105669580A discloses a photocurable resin containing a triazine ring and a preparation method thereof, and the oleic acid structure and the amino resin are modified.
  • the multi-arm bio-based amino acrylate having a hard core soft shell structure is simple in preparation, low in price and strong in photosensitivity, but the hardness of the cured film is low due to the long flexible functional chain structure, and the mechanical strength is low. Further enhance the modification to enhance its application space and value.
  • the present invention provides a high performance etherified bio-based resin and a preparation method thereof.
  • a novel etherified bio-based resin is prepared by etherification reaction of hydroxyethyl cardanol ether with an amino resin, and further modified by secondary etherification of a monohydroxy ether.
  • the prepared bio-based resin can be used in the fields of coatings, adhesives and the like, and the market competitiveness and application value of the cardanol-based materials are improved.
  • a first object of the present invention is to provide an etherified bio-based resin having a structure identical to any one of (a) to (c):
  • the "performance close” refers to the property or application effect of the compound itself, with a variation of no more than 10%.
  • the epoxidation site in (c) is a ring opening esterification reaction with (meth)acrylic acid.
  • the amino resin is an oil-soluble compound obtained by polycondensation of an amino group-containing compound and an aldehyde to obtain a prepolymer, followed by etherification treatment with an alkanol having a carbon chain length of 1 to 9.
  • the amino group-containing compound includes any one of melamine, urea, and benzoguanamine.
  • the aldehyde includes any one of formaldehyde, acetaldehyde, and the like.
  • the amino resin is 10 to 15 parts by weight and the hydroxyethyl cardanol is 30 to 120 parts by weight.
  • the etherification modification reaction comprises:
  • the etherification modification reaction further includes the step (5) and the step (6), wherein
  • etherification modification reaction 10 to 15 parts by weight of the amino resin, 30 to 120 parts by weight of the hydroxyethyl cardanol ether, and 0.1 to 0.3 parts by weight of the catalyst; optionally, a single The hydroxy ether is 20 to 50 parts by weight.
  • etherification modification reaction 10 to 15 parts by weight of the amino resin, 50 to 85 parts by weight of the hydroxyethyl cardanol ether, and 0.1 to 0.3 parts by weight of the catalyst; optionally, a single The hydroxy ether is 20 to 50 parts by weight.
  • the catalyst of the step (1) is p-toluenesulfonic acid, styrenesulfonic acid, sulfamic acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, oxalic acid or phosphoric acid. Any one or more.
  • the reaction solvent in the step (1) is capable of dissolving the reactant, does not participate in the reaction, and can azeotrope with the produced small alcohol molecule (methanol or butanol, etc.) and carry it out of the reaction system.
  • the reaction solvent in the step (1) is an aliphatic alkane having a boiling point between 95 and 130 ° C (such as n-heptane, cycloheptane, n-octane or isooctane), or may be Benzene, toluene, xylene, chlorobenzene, acetonitrile, butyl acetate, and the like.
  • the step (2) is a continuous reaction for 10 to 14 hours.
  • the continuing reaction of the step (3) is continued for a period of 3 to 5 hours.
  • the step (5) monohydroxy ether may be ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethyl Glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monobutyl ether, 1,4-butanediol monomethyl ether or 1,4-butanediol monoethyl ether.
  • step (6) the reaction of step (6) is continued for a period of from 4 to 8 hours.
  • the etherification modification reaction method is specifically:
  • the small molecular alcohol formed in the reaction system is azeotroped with the reaction solvent, thereby removing the small alcohol molecules;
  • the etherified bio-based resin has the structural formula shown in formula (1):
  • R is any of the following:
  • a second object of the present invention is to provide the use of the etherified bio-based resin, including but not limited to the fields of industrial coatings, crosslinking agents and the like.
  • the application is specifically for coatings, cross-linking agents, adhesives, laminates, resins for molding compounds, and treatments for fabrics, paper, leather, and the like.
  • the present invention also provides a coating material comprising the etherified bio-based resin of the present invention.
  • the present invention also provides a 3D printing material or a flame retardant material, and the raw material of the 3D printing material or the flame retardant material includes the etherified bio-based resin of the present invention.
  • the invention selects an industrial derivative of cardanol, hydroxyethyl cardanol ether and an amino resin to obtain an etherified amino resin resin, and the novel bio-based resin can be used as a chemical intermediate for chemical modification in industrial coatings.
  • the field of cross-linking agent and other fields realize its application value; and the presence of a large number of unsaturated double bonds and ether bonds can be further chemically modified as an active site, epoxidation to prepare epoxy resin or further by ring opening reaction of epoxy group Functionalized, such derived resins can be directly applied to the field of coatings and adhesives.
  • petroleum-based amino acrylates have better flexibility due to the introduction of rigid benzene rings and ether bonds.
  • bio-based amino acrylates it has higher mechanical strength and hardness, while having lower viscosity, better flexibility, and a good balance of overall properties.
  • the preparation method of the invention is simple, the cost is low, the reaction conditions are mild, and the controllability is strong.
  • the viscosity of the modified amino resin is significantly reduced, the storage stability of the product is greatly improved, the biocompatibility and environmental degradability are good, and the product performance is stable.
  • Cardanol as a source of abundant renewable resources, has extraordinary significance and potential value for protecting the environment, alleviating energy pressure, promoting energy diversification and sustainable development.
  • the invention utilizes the chemical modification industry of cardanol to transform it into a novel bio-based product with high added value.
  • Example 1 is a schematic view showing the reaction mechanism of Example 1.
  • Example 2 is an infrared diagram of a high methyl etherified melamine formaldehyde resin, hydroxyethyl cardanol ether, and a modified melamine formaldehyde resin prepared in Example 1, wherein HMMM is a high methyl etherified melamine formaldehyde resin, and HCE is a hydroxyethyl group.
  • Cardanol ether, HCEMF is the modified etherified melamine formaldehyde resin prepared in Example 1.
  • Example 3 is a nuclear magnetic hydrogen spectrum diagram of a high methyl etherified melamine formaldehyde resin, hydroxyethyl cardanol ether, and a modified melamine formaldehyde resin prepared in Example 1, wherein HMMM is a high methyl etherified melamine formaldehyde resin, and HCE is a hydroxyl group.
  • Ethyl cardanol ether, HCEMF is the modified etherified melamine formaldehyde resin prepared in Example 1.
  • Example 4 is a nuclear magnetic carbon spectrum of a high methyl etherified melamine formaldehyde resin, hydroxyethyl cardanol ether, and a modified melamine formaldehyde resin prepared in Example 1, wherein HMMM is a high methyl etherified melamine formaldehyde resin, and HCE is a hydroxyl group.
  • Ethyl cardanol ether, HCEMF is the modified etherified melamine formaldehyde resin prepared in Example 1.
  • Figure 1 is the reaction mechanism of Example 1.
  • the highly reactive methoxymethyl group in the high methyl etherified melamine formaldehyde resin can undergo an ether exchange reaction with a hydroxyl group-containing hydroxyethyl cardanol ether under the action of an acidic catalyst under heating.
  • the methanol formed in the reaction can be slowly separated from the reaction system to drive the reaction to proceed, and hydroxyethyl cardanol modified etherified melamine formaldehyde resin with different degrees of etherification is formed.
  • Example 2 is an infrared spectrum of a high methyl etherified melamine formaldehyde resin, hydroxyethyl cardanol ether, and a modified melamine formaldehyde resin prepared in Example 1, and the hydroxyl absorption peak at 3400 cm -1 is significantly weakened, 1548 cm -1 and 1486 cm -
  • the characteristic absorption peak of the triazine ring bond appeared at one position, the infrared characteristic absorption peak of the ether bond appeared at 1085 cm -1 and 1025 cm -1 , and the infrared characteristic absorption peak of the external vibration of the triazine ring skeleton appeared at 816 cm -1 .
  • the successful completion of the ether exchange reaction was confirmed.
  • FIG. 3 is a nuclear magnetic resonance spectrum of a high methyl etherified melamine formaldehyde resin, hydroxyethyl cardanol ether, and a modified melamine formaldehyde resin prepared in Example 1, and an absorption peak appearing at ⁇ 5.01 to 5.12 is attributed to Ha, ⁇ 3.
  • the absorption peak appearing at .29 ⁇ 3.45 is attributed to Hb, and the absorption peak appearing at ⁇ 4.89 ⁇ 4.00 belongs to Hc.
  • the NMR spectrum proves that hydroxyethyl cardanol ether has successfully etherted with high methyl etherified melamine formaldehyde resin. Exchange reactions.
  • Example 4 is a nuclear magnetic carbon spectrum of a high methyl etherified melamine formaldehyde resin, hydroxyethyl cardanol ether, and a modified melamine formaldehyde resin prepared in Example 1, and an absorption peak appearing at ⁇ 166.6 to 166.9 is assigned to c, ⁇ 77
  • the absorption peak appearing at .6-76.6 is attributed to b, and the absorption peak appearing at ⁇ 56.1 ⁇ 55.8 belongs to a.
  • the NMR spectrum proves that hydroxyethyl cardanol ether successfully reacts with high methyl etherified melamine formaldehyde resin. Exchange reactions.
  • the monohydroxy ether (ethylene glycol monomethyl ether) was subjected to secondary mixed etherification modification, and the viscosity of the obtained resin was compared with the resin obtained by further treating without adding ethylene glycol monomethyl ether. It dropped from 1312 mPa ⁇ s to 1176 mPa ⁇ s.
  • the high methyl etherified urea formaldehyde resin is obtained by methylolation reaction of an amino group in urea with formaldehyde, followed by etherification modification with methanol, and the main reactive group in the resin is -CH 2 -O.
  • -CH 3 under the action of an acidic catalyst, can also undergo an ether exchange reaction with hydroxyethyl cardanol ether, and the methanol formed during the reaction is azeotroped with the solvent to be taken out of the reaction system to promote the reaction.
  • the structure was confirmed by infrared, nuclear magnetic resonance spectroscopy and nuclear magnetic carbon spectroscopy.
  • the high methyl etherified urea-formaldehyde resin was successfully exchanged with hydroxyethyl cardanol ether.
  • the high methyl etherified benzene melamine formaldehyde resin is obtained by methylolation reaction of the amino group of phenyl melamine with formaldehyde, and then reacted with methanol to carry out etherification modification.
  • the main reactive group in the resin is -CH. 2 -O-CH 3 can also undergo an ether exchange reaction with hydroxyethyl cardanol by the action of an acidic catalyst, and the methanol formed during the reaction will be azeotroped with the solvent to be taken out of the reaction system to promote the reaction.
  • the structure was confirmed by infrared, nuclear magnetic resonance spectroscopy and nuclear magnetic carbon spectroscopy.
  • the high methyl etherified benzene melamine formaldehyde resin was successfully exchanged with hydroxyethyl cardanol ether.
  • the properties of the resins prepared in Examples 1-5 were measured. Among them, the appearance was observed by visual observation, the viscosity was tested according to GB/T7193-2008, and the free formaldehyde content in the resin was tested according to GB5544-85.
  • Example 1 Light brown transparent liquid >99% 1200-1400 ⁇ 0.1%
  • Example 2 Light brown transparent liquid >99% 1000-1200 ⁇ 0.1%
  • Example 3 Light brown transparent liquid >99% 3400-3800 ⁇ 0.1%
  • Example 4 Light brown transparent liquid >99% 3200-3400 ⁇ 0.1%
  • Example 5 Light brown transparent liquid >99% 2300-2700 ⁇ 0.1% Control 1 Dark brown transparent liquid __ 4500-5600 __ Control 2 Colorless or light yellow transparent liquid __ 400-800 ⁇ 1%
  • the products prepared in the examples 1-5 can be dissolved in an organic solvent such as dichloromethane, chloroform, ethanol, acetone, ethyl acetate, toluene, diethyl ether or xylene, and have good solubility and are stored at room temperature. 3-6 months, the product does not precipitate without precipitation, the viscosity can be kept unchanged, has better storage stability, and the non-conjugated double bond in the unsaturated fatty chain has higher reactivity and can be used for further chemical modification. .
  • an organic solvent such as dichloromethane, chloroform, ethanol, acetone, ethyl acetate, toluene, diethyl ether or xylene
  • Control 1 is a triazine ring-containing photocurable resin of application No. 201610010125.1, the viscosity of which is tested by a rheometer, and a 25 mm parallel steel plate is used to measure the viscosity at different shear rates of the sample, and the viscosity is selected as 10 rad/s.
  • Control 2 is "Ying Mingyou. Synthesis of new photosensitive prepolymer and its application in ink [D]. Jiangnan University, 2008.” Amino acrylic resin in 2.3.1, viscosity is rotated with NDJ-79 The viscometer was measured and measured at 25 ° C, and the rotor was rotated for 1 min and the indicated value was stabilized (ie, GB/T 7193-2008 viscosity). Although the viscosity of the product in Control 2 is low, the raw material is derived from petroleum-based materials and is difficult to be biodegraded. The natural degradation cycle of the waste is easy to cause environmental pollution, and the hardness of the cured film is too high (6H to 7H), and the brittleness is large and flexible. Poor, not suitable for flexible substrate coatings such as fabrics and paper.
  • the etherified bio-based amino resin obtained in Example 2 and the NX47 type alkyd resin (Qingyuan Nanxing Chemical Co., Ltd.) were compounded in different mass ratios, and 0.2% by weight of the resin was added to the drier.
  • the amount of methylene chloride as a solvent (control solid content is 77%), after film coating, curing at 90 ° C for 10h for sampling and testing, according to GB/T 1720-1979 to detect the adhesion of the coating; BYK micro gloss meter test coating
  • the gloss of the layer; the pencil hardness of the coating was tested according to GB/T 6739-2006; the hardness of the pendulum of the coating was measured by BYK pendulum hardness tester according to ASTM D4366.
  • the main technical indexes are shown in Table 2.
  • the white solid was removed by suction filtration, and the resulting solution was washed with a saturated sodium sulfite solution until the aqueous phase was not discolored, and then washed twice with saturated sodium bicarbonate solution and saturated brine, and the solvent was removed by rotation. It was dried in a vacuum oven at 45 ° C for 12 h to obtain an etherified bio-based amino epoxy resin.
  • the etherified bio-based amino epoxy resin obtained in this example was sampled and tested, and the main technical indexes thereof are shown in Table 3.
  • the etherified bio-based amino epoxy resin obtained in the present example and methyl hexahydrophthalic anhydride were coated on the Q-panel by a frame type film applicator according to the ratio of the epoxy group to the acid anhydride molar ratio (1:0.4).
  • Iron plate curing at 120 ° C for 12 hours, sampling and testing the obtained paint film, testing the adhesion of the coating according to GB/T 9286-1998; testing the gloss of the coating with BYK micro gloss meter; according to GB/T 6739-2006 Test the pencil hardness of the coating; the pendulum hardness of the coating was measured by a BYK pendulum hardness tester in accordance with ASTM D4366.
  • the test performance results are shown in Table 4.
  • Control 1 is the EHMMLO resin in application number 201610010125.1.
  • the adhesion of the coating was tested according to GB/T 1720-1979; the gloss of the coating was tested by BYK micro-gloss meter; the pencil hardness of the coating was tested according to GB/T 6739-2006; the hardness was measured by BYK pendulum hardness tester according to ASTM D4366. The pendulum hardness of the coating.
  • the ratio of the epoxy group bio-based amino epoxy resin, the epoxy soybean oil (Adamas reagent Co., Ltd.) and the methyl hexahydrophthalic anhydride obtained in this example according to the molar ratio of the epoxy group to the acid anhydride (1:0.4), It is coated on Q-panel iron plate by frame type applicator and can be dried by curing at 120 °C for 2h.
  • epoxy soybean oil can not reach surface dryness after curing at 120 °C for 24h, and the curing temperature needs to reach 180°C. It shows that the etherified bio-based amino epoxy resin obtained in the present embodiment has higher reactivity and curing speed.
  • the etherified bio-based amino epoxy acrylate obtained in this example was sampled and tested, and the main technical indexes thereof are shown in Table 5.
  • the etherified bio-based amino epoxy acrylate obtained in this example was added to a 3 wt% photoinitiator I-184 for photocuring, and the obtained paint film was sampled and tested, and the coating was tested according to GB/T 1720-1979. Adhesion; the gloss of the coating was tested by BYK micro-gloss meter; the pencil hardness of the coating was tested according to GB/T 6739-2006; the pendulum hardness of the coating was measured by BYK pendulum hardness tester according to ASTM D4366. The test performance results are shown in Table 6.
  • Control 1 is the photo-curing resin containing triazine ring in application No. 201610010125.1, and the adhesion of the coating is tested according to GB/T 1720-1979; the gloss of the coating is tested by BYK micro-gloss meter; according to GB/T 6739-2006 The pencil hardness of the coating was tested; the pendulum hardness of the coating was measured using a BYK pendulum hardness tester in accordance with ASTM D4366. It is significantly lower than the etherified bio-based amino epoxy acrylate obtained in this example because of the lack of rigid group pendulum hardness and Tg.
  • Control 2 is "Ying Mingyou. Synthesis of a novel photosensitive prepolymer and its application in inks [D]. Jiangnan University, 2008.” Petroleum-based aminoacrylic resin of 3.3.5, coated with QHQ-A
  • the film pencil scratch hardness tester (Tianjin Material Testing Machine Factory) tested the hardness of the coating film, and tested its coating adhesion using a QFZ-II type film adhesion tester (Tianjin Kelian Material Testing Machine Factory).
  • the etherified bio-based amino epoxy acrylate obtained in the present example has good biodegradability with respect to the amino acrylate of Control 2, is environmentally friendly, and has a more balanced coating property.

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Abstract

一种高性能醚化生物基树脂，首先以氨基树脂与羟乙基腰果酚醚作为原料，在催化剂作用下进行醚交换得到高生物基含量改性氨基树脂，可再加入一定量的单羟基低级醚制得更低粘度、稳定性好的混醚化氨基树脂。该制备方法简单、成本低、反应条件温和，可控性强，合成的生物基混醚化氨基树脂固含高，粘度低，具有良好的生物可降解性，产品性能稳定，并且可作为化工中间体应用于工业涂料领域。

Description

一种高性能醚化生物基树脂及其制备方法 技术领域
本发明涉及一种高性能醚化生物基树脂及其制备方法，属于合成树脂技术领域。
背景技术
氨基树脂是指由含氨基(-NH 2)的化合物与甲醛进行羟甲基化反应后，再与低级醇反应进行醚化改性而得到的一类具有高交联活性的热固性树脂。通常以氨基树脂作为交联剂而得的涂膜具有高硬度、高光泽度、保色性佳、耐化学性和耐候性好的优点，因此被广泛应用于涂料工业、皮革鞣剂、胶黏剂、阻燃材料等领域。
目前，市场上醚化三聚氰胺树脂产品较多，合成技术已很成熟。三聚氰胺甲醛树脂中含有大量-CH 2OH和-NH-基团，极性很强，很不稳定，且不溶于有机溶剂，因此工业上使用低级醇对其进行醚化改性，将-CH 2OH基团醚化，降低其极性，改善其溶解性。由于合成醚化三聚氰胺甲醛树脂的原料中含有甲醛，产物中不可避免的含有一定量的亚甲基。亚甲基在高温加热时会释放出甲醛。所以HMMM产品在应用中也会有少量甲醛释放。同时亚氨基很活泼，不稳定，最易发生自交联反应，贮存稳定性差。通常工业生产的醚化三聚氰胺树脂含有一定量的溶剂，醚化度低也会降低固含量。由上可知，醚化三聚氰胺树脂存在着储存稳定性差、游离甲醛含量高、固含量低、气味大等问题，危害环境的同时长期接触还会对人体健康造成潜在的危害性，使其在涂料、油墨中的应用受到了一定程度的限制。
为了解决上述的问题，有研究者选择在氨基树脂结构中引入光敏基团制备氨基丙烯酸酯，例如“应明友.新型光敏性预聚物的合成及其在油墨中的应用[D].江南大学,2008.”中合成了可光固化的石油基氨基丙烯酸树脂，从而达到提升储存稳定性和降低甲醛含量的效果，然而这种树脂硬度过高导致刚性有余而柔韧性不足，限制其在某些柔性基材上的应用；本课题组之前也进行过相关研究，例如在CN 105669580A中公开了一种含三嗪环的光固化树脂及其制备方法，将油酸结构与氨基树脂通过改性制得具有硬核软壳结构的多臂生物基氨基丙烯酸酯，制备方法简单、价格便宜、光敏性强，但是由于分子结构含有长的柔性脂肪链，导致固化膜硬度，力学强度偏低，需要进一步增强改性提升其应用空间与价值。
因此，有必要开发能改善溶解性、高固含、低粘度、存储稳定性、反应活性好的树脂，并且保证该树脂的固化膜能很好地兼顾硬度与柔韧性，在综合性能上达到更好的均衡。
发明内容
针对现有技术存在的上述问题，本发明提供了一种高性能醚化生物基树脂及其制备方法。 本发明将羟乙基腰果酚醚与氨基树脂通过醚化反应，制备了新型醚化生物基树脂，进一步地，通过单羟基醚二次醚化改性。制备得到的生物基树脂可用于涂料、胶黏剂等领域，提高了腰果酚基材料的市场竞争力和应用价值。
本发明的第一个目的是提供一种醚化生物基树脂，其结构与(a)～(c)中的任意一个化合物一致：
(b)使用羟乙基腰果酚醚对氨基树脂进行醚化改性反应得到的化合物；
(b)在(a)所得化合物的基础上，使与羟乙基腰果酚醚对应的脂肪链上的至少1个不饱和双键发生环氧化反应而得到的化合物；
(c)在(b)所得化合物的基础上，使环氧化位点发生开环酯化反应而得到的化合物；
(d)在(a)、(b)或(c)所得化合物的基础上进一步发生基团取代而得到的与对应(a)、(b)或(c)所得化合物性能接近的化合物。
在一种实施方式中，所述“性能接近”是指化合物本身特性或者应用效果，变化幅度不超过10％。
在一种实施方式中，所述(c)中环氧化位点是与(甲基)丙烯酸发生开环酯化反应。
在一种实施方式中，所述氨基树脂为含有氨基的化合物与醛类经缩聚制得预聚体，再经碳链长度为1～9的烷醇进行醚化处理得到的油溶性化合物。
在一种实施方式中，所述含有氨基的化合物包括三聚氰胺、尿素和苯代三聚氰胺等中的任意一种。
在一种实施方式中，所述醛类包括甲醛、乙醛等中的任意一种。
在一种实施方式中，氨基树脂的份数为10～15重量份、羟乙基腰果酚醚30～120重量份。
在一种实施方式中，所述醚化改性反应，包括：
(2)将氨基树脂、羟乙基腰果酚醚、催化剂和反应溶剂，按照一定比例混合，升温至90～125℃；
(2)反应一段时间，使反应体系中生成的小分子醇类与反应溶剂共沸，从而脱出醇类小分子；
(3)继续反应一段时间后冷却、脱除反应溶剂；
(4)对上一步所得产物进行洗涤，除去催化剂和未反应的原料，脱除溶剂、干燥，得产品。
在一种实施方式中，所述醚化改性反应，还包括步骤(5)和步骤(6)，其中，
(5)将上一步所得产物与单羟基醚、催化剂混合，升温至90～130℃；
(6)反应一段时间后，降温、除去未反应的单羟基醚，干燥，得产品。
在一种实施方式中，所述醚化改性反应中，氨基树脂10～15重量份、羟乙基腰果酚醚30-120重量份、催化剂0.1～0.3重量份；可选地，还包括单羟基醚20～50重量份。
在一种实施方式中，所述醚化改性反应中，氨基树脂10～15重量份、羟乙基腰果酚醚50～85重量份、催化剂0.1～0.3重量份；可选地，还包括单羟基醚20～50重量份。
在一种实施方式中，所述步骤(1)催化剂为对甲苯磺酸、苯乙烯磺酸、氨基磺酸、苯甲酸、苯乙酸、邻苯二甲酸、对苯二甲酸、草酸或磷酸中的任意一种或多种。
在一种实施方式中，所述步骤(1)反应溶剂能溶解反应物，不参与反应，且能与生成的醇类小分子(甲醇或丁醇等)共沸，将其带出反应体系。
在一种实施方式中，所述步骤(1)反应溶剂为沸点在95～130℃之间的脂肪族烷烃(比如正庚烷、环庚烷、正辛烷或异辛烷)，还可以是苯、甲苯、二甲苯、氯苯、乙腈、乙酸丁酯等。
在一种实施方式中，所述步骤(2)是持续反应10～14小时。
在一种实施方式中，所述步骤(3)的继续反应一段时间是继续升温反应3～5小时。
在一种实施方式中，所述步骤(5)单羟基醚可以是乙二醇单甲醚、乙二醇单乙醚、乙二醇单丁醚、丙二醇单甲醚、丙二醇单乙醚、丙二醇单丁醚、二乙二醇单甲醚、二乙二醇单乙醚、二乙二醇单丁醚、三乙二醇单甲醚、三乙二醇单乙醚、三乙二醇单丁醚、四乙二醇单甲醚、四乙二醇单乙醚、四乙二醇单丁醚、1,4-丁二醇单甲醚或1,4-丁二醇单乙醚等。
在一种实施方式中，步骤(6)的反应一段时间是持续反应4～8小时。
在一种实施方式中，所述醚化改性反应方法具体是：
(1)投入氨基树脂、羟乙基腰果酚醚、催化剂和反应溶剂，然后缓慢升温至90～125℃；
(2)持续10～14小时，使反应体系中生成的小分子醇类与反应溶剂共沸，从而脱出醇类小分子；
(3)继续升温反应3～5小时，反应结束后停止加热并继续搅拌冷却至室温，脱除烷烃溶剂；
(4)对所得产物进行多次洗涤除去催化剂和未反应的原料，脱除溶剂，干燥。
(5)将步骤(4)所得产物与单羟基醚和催化剂投入反应釜，缓慢升温至90～130℃；
(6)持续反应4～8小时后降温至室温，减压蒸馏除去未反应的单羟基醚，真空干燥，即得。
在一种实施方式中，醚化生物基树脂，其结构式如式(1)所示：
Figure PCTCN2018072054-appb-000001
其中，R为以下任意一种：
Figure PCTCN2018072054-appb-000002
本发明的第二个目的是提供所述醚化生物基树脂的应用，包括但不限于工业涂料、交联剂等领域。
在一种实施方式中，所述应用具体是用于涂料、交联剂、胶粘剂、层压材料、模塑料用树脂，又可作织物、纸张、皮革等的处理剂。
本发明还提供一种涂料，其原料包含本发明的醚化生物基树脂。
本发明还提供一种3D打印材料或阻燃材料，所述3D打印材料或阻燃材料的原料包括本发明的醚化生物基树脂。
本发明的优点和效果：
(1)本发明选用腰果酚的工业衍生物羟乙基腰果酚醚与氨基树脂制得醚化氨基树脂树脂，这种新型生物基基树脂可以作为化工中间体通过化学改性应用于工业涂料、交联剂等领域实现其应用价值；而大量不饱和双键及醚键的存在可作为活性位点进一步化学改性，进行环氧化制备环氧树脂或进一步通过对环氧基的开环反应官能化，这样的衍生树脂可直接应用于涂料及粘合剂领域。相对于之前报告(新型光敏性预聚物的合成及其在油墨中的应用[D].)的石油基氨基丙烯酸酯具有更好的柔韧性，由于刚性苯环和醚键的引入，使其相对于先前报 告的生物基氨基丙烯酸酯具有更高的力学强度与硬度，同时粘度低，具有更好柔韧性，综合性能上可以达到很好的均衡。
(2)本发明的制备方法简单，成本低，反应条件温和，可控性强。改性后氨基树脂的粘度显著降低，产品的耐贮存性得到极大提升，具有良好的生物相容性及环保可降解性，产品性能稳定。
(3)腰果酚作为来源丰富的可再生资源，对于保护环境，缓解能源压力，促进能源向多元化发展以及可持续发展等都具有非凡的意义及潜在价值。本发明利用腰果酚的化学改性工业，使之转化成为具有高附加值的新型生物基产品。
附图说明
图1为实施例1的反应机理的示意图。
图2为高甲醚化三聚氰胺甲醛树脂、羟乙基腰果酚醚、实施例1中制备的改性三聚氰胺甲醛树脂的红外图；其中，HMMM为高甲醚化三聚氰胺甲醛树脂，HCE为羟乙基腰果酚醚，HCEMF为实施例1制备的改性醚化三聚氰胺甲醛树脂。
图3为高甲醚化三聚氰胺甲醛树脂、羟乙基腰果酚醚、实施例1中制备的改性三聚氰胺甲醛树脂的核磁氢谱图；其中，HMMM为高甲醚化三聚氰胺甲醛树脂，HCE为羟乙基腰果酚醚，HCEMF为实施例1制备的改性醚化三聚氰胺甲醛树脂。
图4为高甲醚化三聚氰胺甲醛树脂、羟乙基腰果酚醚、实施例1中制备的改性三聚氰胺甲醛树脂的核磁碳谱图；其中，HMMM为高甲醚化三聚氰胺甲醛树脂，HCE为羟乙基腰果酚醚，HCEMF为实施例1制备的改性醚化三聚氰胺甲醛树脂。
具体实施方案
下面是对本发明进行具体描述。
实施例1
(1)将23.426g高甲醚化三聚氰胺甲醛树脂(济南三强化工有限公司，粘度7300mPa·s)、124.034g羟乙基腰果酚醚、0.468g对甲苯磺酸、12g正辛烷加入装有动力搅拌棒、冷凝回流管、温度计和装有正辛烷分水器的250mL四口烧瓶中；
(2)升温前通入干燥气体，1小时内缓慢升高温度至110℃微回流，持续反应14小时，使正辛烷与反应物中生成的甲醇形成共沸物，以缓慢从反应体系中脱除醇类小分子，反应14小时后再升温至125℃继续反应4小时；
(3)反应结束后停止加热并继续搅拌冷却至室温，减压蒸馏脱除体系内残留的正庚烷，得到产物A；
(4)用乙腈对产物A进行多次洗涤除去未反应的催化剂(对甲苯磺酸)与原料，减压蒸馏，置于真空烘箱中干燥24小时，得到醚化改性三聚氰胺甲醛树脂(粘度1312mPa·s)。
图1为实施例1的反应机理，高甲醚化三聚氰胺甲醛树脂中高活性的甲氧甲基在加热的情况下可与含有羟基的羟乙基腰果酚醚在酸性催化剂的作用下发生醚交换反应，反应中生成的甲醇可缓慢脱离出反应体系以推动反应继续进行，生成不同醚化程度的羟乙基腰果酚改性醚化三聚氰胺甲醛树脂。
图2为高甲醚化三聚氰胺甲醛树脂、羟乙基腰果酚醚、实施例1中制备的改性三聚氰胺甲醛树脂的红外图谱，3400cm -1处的羟基吸收峰明显减弱，1548cm -1及1486cm -1处出现了三嗪环键的特征吸收峰，1085cm -1及1025cm -1处出现了醚键的红外特征吸收峰，816cm -1处出现了三嗪环骨架外面弯曲振动的红外特征吸收峰，证实了醚交换反应的成功进行。
图3为高甲醚化三聚氰胺甲醛树脂、羟乙基腰果酚醚、实施例1中制备的改性三聚氰胺甲醛树脂的核磁氢谱图，δ5.01～5.12处出现的吸收峰归属于Ha，δ3.29～3.45处出现的吸收峰归属于Hb，δ4.89～4.00处出现的吸收峰归属于Hc，核磁谱图证明了羟乙基腰果酚醚成功与高甲醚化三聚氰胺甲醛树脂发生了醚交换反应。
图4为高甲醚化三聚氰胺甲醛树脂、羟乙基腰果酚醚、实施例1中制备的改性三聚氰胺甲醛树脂的核磁碳谱图，δ166.6～166.9处出现的吸收峰归属于c，δ77.6～76.6处出现的吸收峰归属于b，δ56.1～55.8处出现的吸收峰归属于a，核磁谱图证明了羟乙基腰果酚醚成功与高甲醚化三聚氰胺甲醛树脂发生了醚交换反应。
结合图1-4，能够确认合成了如下化合物
Figure PCTCN2018072054-appb-000003
其中，R为
Figure PCTCN2018072054-appb-000004
实施例2
(1)将3.254g高甲醚化三聚氰胺甲醛树脂(济南三强化工有限公司)、17.227g羟乙 基腰果酚醚、0.069g对甲苯磺酸、2.146g异辛烷加入装有动力搅拌棒、冷凝回流管、温度计和装有正庚烷分水器的100mL四口烧瓶中；
(2)升温前通入干燥气体，1.5小时内缓慢升高温度至105℃微回流，持续反应13小时,使异辛烷与反应物中生成的丁醇形成共沸物，以缓慢从反应体系中脱除醇类小分子；
(3)反应结束后停止加热并继续搅拌冷却至室温，减压蒸馏脱除体系内残留的异辛烷，得到产物A；
(4)用乙腈对产物A进行多次洗涤除去未反应催化剂对甲苯磺酸与原料，减压蒸馏除去体系内残留的乙腈后，置于真空烘箱中干燥24小时，得到产物B。
(5)取10.452g产物B、4.235g乙二醇单甲醚、0.184g对甲苯磺酸投入装有动力搅拌棒、冷凝回流管和温度计的100mL三口烧瓶中，缓慢升温至115℃；
(6)持续反应5小时，降温至室温后减压蒸馏除去未反应的乙二醇单甲醚，真空干燥24小时，即得混醚化改性三聚氰胺甲醛树脂。
本实施例，用了单羟基醚(乙二醇单甲醚)对其进行了二次混醚化改性，与不添加乙二醇单甲醚进行进一步处理得到的树脂相比，所得树脂粘度从1312mPa·s下降到1176mPa·s。
实施例3
(1)将23.614g高甲醚化脲甲醛树脂、137.816g羟乙基腰果酚醚、0.274g对甲苯磺酸、12g正辛烷加入装有动力搅拌棒、冷凝回流管、温度计和装有正辛烷分水器的100mL四口烧瓶中；
(2)升温前通入干燥气体，1.5小时内缓慢升高温度至110℃微回流，持续反应12小时,使正辛烷与反应物中生成的甲醇形成共沸物，以缓慢从反应体系中脱除醇类小分子；
(3)反应结束后停止加热并继续搅拌冷却至室温，减压蒸馏脱除体系内残留的正辛烷，得到产物A；
(4)对产物A进行多次洗涤除去未反应的催化剂及原料，减压蒸馏，置于真空烘箱中干燥24小时，得到产物改性脲甲醛树脂。
高甲醚化脲甲醛树脂是由尿素中的氨基基团与甲醛进行羟甲基化反应后，再与甲醇反应进行醚化改性而得到，树脂中的主要反应基团为-CH 2-O-CH 3，在酸性催化剂的作用下同样能与羟乙基腰果酚醚发生醚交换反应，反应过程中生成的甲醇会与溶剂共沸从而被带出反应体系促进反应的进行。经红外、核磁氢谱、核磁碳谱进行结构确认，高甲醚化脲甲醛树脂成功与羟乙基腰果酚醚发生了醚交换反应。
实施例4
(1)将23.614g高甲醚化脲甲醛树脂、137.816g羟乙基腰果酚醚、0.274g对甲苯磺酸、12g正辛烷加入装有动力搅拌棒、冷凝回流管、温度计和装有正辛烷分水器的100mL四口烧瓶中；
(2)升温前通入干燥气体，1.5小时内缓慢升高温度至110℃微回流，持续反应12小时,使正辛烷与反应物中生成的甲醇形成共沸物，以缓慢从反应体系中脱除醇类小分子；
(3)反应结束后停止加热并继续搅拌冷却至室温，减压蒸馏脱除体系内残留的正辛烷，得到产物A；
(4)对产物A进行多次洗涤除去未反应的催化剂原料，减压蒸馏，置于真空烘箱中干燥24小时，得到产物B。
(5)取40g产物B，56g乙二醇单甲醚，0.5g对甲苯磺酸，投入装有动力搅拌棒、冷凝回流管和温度计的200mL三口烧瓶中，缓慢升温至120℃；
(6)持续反应4小时，降温至室温后减压蒸馏除去未反应的乙二醇单甲醚，真空干燥24小时，即得混醚化改性脲甲醛树脂。
实施例5
(1)将36.319g高甲醚化苯代三聚氰胺甲醛树脂、137.816g羟乙基腰果酚醚、0.274g对甲苯磺酸、19g正辛烷加入装有动力搅拌棒、冷凝回流管、温度计和装有正辛烷分水器的100mL四口烧瓶中；
(2)升温前通入干燥气体，1.5小时内缓慢升高温度至115℃微回流，持续反应12小时,使正辛烷与反应物中生成的甲醇形成共沸物，以缓慢从反应体系中脱除醇类小分子；
(3)反应结束后停止加热并继续搅拌冷却至室温，减压蒸馏脱除体系内残留的正辛烷，得到产物A；
(4)对产物A进行多次洗涤除去未反应的催化剂及原料，减压蒸馏，置于真空烘箱中干燥24小时，得到产物改性苯代三聚氰胺甲醛树脂。
高甲醚化苯代三聚氰胺甲醛树脂是由苯代三聚氰胺的氨基基团与甲醛进行羟甲基化反应后，再与甲醇反应进行醚化改性而得到，树脂中的主要反应基团为-CH 2-O-CH 3，在酸性催化剂的作用下同样能与羟乙基腰果酚醚发生醚交换反应，反应过程中生成的甲醇会与溶剂共沸从而被带出反应体系促进反应的进行。经红外、核磁氢谱、核磁碳谱进行结构确认，高甲醚化苯代三聚氰胺甲醛树脂成功与羟乙基腰果酚醚发生了醚交换反应。
实施例6
对实施例1-5制备得到的树脂进行性能测定。其中，外观通过目测观察，粘度按照GB/T7193-2008测试，树脂中游离甲醛含量按照GB5544-85测试。
表1 不同树脂性能比较
外观 固含 粘度(25℃，mpa.s) 甲醛含量
实施例1 浅棕色透明液体 >99％ 1200-1400 <0.1％
实施例2 浅棕色透明液体 >99％ 1000-1200 <0.1％
实施例3 浅棕色透明液体 >99％ 3400-3800 <0.1％
实施例4 浅棕色透明液体 >99％ 3200-3400 <0.1％
实施例5 浅棕色透明液体 >99％ 2300-2700 <0.1％
对照1 深棕色透明液体 __ 4500-5600 __
对照2 无色或浅黄色透明液体 __ 400-800 <1％
实施案例1-5中制备的产物均可溶于二氯甲烷、三氯甲烷、乙醇、丙酮、乙酸乙酯、甲苯、乙醚、二甲苯等有机溶剂，具有较好的溶解性，在室温下存储3-6个月，产品不分层不沉淀，粘度能保持不变，具有较佳的储存稳定性，不饱和脂肪链中的非共轭双键具有较高反应活性，可用于进一步化学改性。
对照1是申请号201610010125.1中的含三嗪环的光固化树脂，其粘度采用流变仪测试，选用25mm平行钢板，测定样品不同剪切速率下的粘度，选取10rad/s时作为样品粘度。
对照2是“应明友.新型光敏性预聚物的合成及其在油墨中的应用[D].江南大学,2008.”里2.3.1的氨基丙烯酸树脂，粘度是用NDJ-79型旋转粘度计测定，在25℃下测定，记录转子旋转1min并且稳定的指示数值(即GB/T 7193-2008测黏度)。虽然对照2中的产品粘度低，但是其原料来源于石油基，难以生物降解，其废弃物自然降解周期长容易造成环境污染，同时其固化膜硬度过高(6H～7H)，脆性大，柔韧性差，不适合应用于织物及纸张等柔性基材涂层。
实施例7
对实施例2中所获得的醚化生物基氨基树脂与NX47型醇酸树脂(清远市南星化工有限公司)进行不同质量比例的复配，并加入占树脂0.2wt％的催干剂，加入一定量的二氯甲烷作为溶剂(控制固含为77％)，涂膜后在90℃下固化10h进行取样检测，按GB/T 1720—1979检测涂层的附着力；采用BYK微型光泽仪测试涂层的光泽度；按GB/T 6739-2006测试涂层 的铅笔硬度；采用BYK摆杆硬度仪按ASTM D4366测定涂层的摆杆硬度，其主要技术指标如表2所示。
表2 醚化生物基氨基树脂与醇酸树脂复配体系的主要技术指标
Figure PCTCN2018072054-appb-000005
实施例8：醚化生物基氨基环氧树脂
(1)将23.426g高甲醚化三聚氰胺甲醛树脂(济南三强化工有限公司)、124.034g羟乙基腰果酚醚、0.468g对甲苯磺酸、12g正辛烷加入装有动力搅拌棒、冷凝回流管、温度计和装有正辛烷分水器的250mL四口烧瓶中；
(2)升温前通入干燥气体，1小时内缓慢升高温度至110℃微回流，持续反应14小时，使正辛烷与反应物中生成的甲醇形成共沸物，以缓慢从反应体系中脱除醇类小分子，反应14小时后再升温至125℃继续反应4小时；
(3)反应结束后停止加热并继续搅拌冷却至室温，减压蒸馏脱除体系内残留的正庚烷，得到产物A；
(4)对产物A进行多次洗涤除去未反应的催化剂与原料，减压蒸馏，置于真空烘箱中干燥24小时，得到产物B。
(5)将15.50g产物B加入到装配有温度计，机械搅拌器的250mL三口圆底烧瓶中，通过恒压漏斗缓慢滴加溶有22.80g间氯过氧苯甲酸(有效成分含量85％，按照与不饱和双键等摩尔量投料)的二氯甲烷。在0℃冰水浴下反应3h。反应结束后将白色固体抽滤除去后，将所得溶液使用饱和的亚硫酸钠溶液洗涤至水相不使淀粉石蕊试纸变色、再用饱和碳酸氢钠溶液及饱和食盐水各洗涤2次，旋转除去溶剂，在45℃真空干燥箱干燥12h，得到醚化生物基氨基环氧树脂。
对本实施例所获得的醚化生物基氨基环氧树脂进行取样检测，其主要技术指标如表3所示。
表3 醚化生物基氨基环氧树脂的主要技术指标
性能 技术指标 测试标准(方法)
外观 棕色透明状液体 目测
粘度(25℃，mpa.s) 2600-2900 GB/T7193-2008
游离甲醛含量 <0.1％ GB5544-85
固含 >99％ GB/T7193.3-1987
以本实施例所获得的醚化生物基氨基环氧树脂与甲基六氢苯酐按照环氧基团与酸酐摩尔比(1:0.4)的比例，利用框架式涂膜器涂布于Q-panel铁板上，120℃固化12小时，对制得的漆膜进行取样检测，按GB/T 9286-1998检测涂层的附着力；采用BYK微型光泽仪测试涂层的光泽度；按GB/T 6739-2006测试涂层的铅笔硬度；采用BYK摆杆硬度仪按ASTM D4366测定涂层的摆杆硬度。其检测性能结果如表4所示。
表4 不同环氧树脂-酸酐固化体系的性能指标
检验项目 环氧基团：酸酐 光泽度(60°) 铅笔硬度 摆杆硬度(s) 附着力
实施例8 1:0.4 112±4 6H 113±4 0
对照1 1:0.4 104±6 6H 97±3 0
对照1是申请号201610010125.1中的EHMMLO树脂。按GB/T 1720—1979检测涂层的附着力；采用BYK微型光泽仪测试涂层的光泽度；按GB/T 6739-2006测试涂层的铅笔硬度；采用BYK摆杆硬度仪按ASTM D4366测定涂层的摆杆硬度。
本实施例所获得的醚化生物基氨基环氧树脂、环氧大豆油(阿达玛斯试剂有限公司)与甲基六氢苯酐按照环氧基团与酸酐摩尔比(1:0.4)的比例，利用框架式涂膜器涂布于Q-panel铁板上，120℃固化2h即可达到表干，而环氧大豆油在120℃温度下固化24h仍不能达到表干，固化温度需要达到180℃，表明本实施例所获得的醚化生物基氨基环氧树脂具有较高的反应活性与固化速度。
实施例9：醚化生物基氨基环氧丙烯酸酯
在实施例8得到的醚化生物基氨基环氧树脂(产物C)的基础上，进行如下反应：
将15g产物C加入1wt％的催化剂2-乙基己酸铬，0.1wt％的阻聚剂对苯二酚，加入到装有磁力搅拌及温度计的三口烧瓶中，使用油浴锅将混合物升温至90℃后，通过滴液漏斗滴加2.945g的丙烯酸，0.5h内滴完，继续升温至110℃持续搅拌反应，反应6h后停止反应，即得 醚化生物基氨基环氧丙烯酸酯。
对本实施例所获得的醚化生物基氨基环氧丙烯酸酯进行取样检测，其主要技术指标如表5所示。
表5 醚化生物基氨基环氧丙烯酸酯的主要技术指标
性能 技术指标 测试标准(方法)
外观 深棕色透明状液体 目测
粘度(25℃，mpa.s) 26000-38000 GB/T7193-2008
游离甲醛含量 <0.1％ GB5544-85
以本实施例所获得的醚化生物基氨基环氧丙烯酸酯加入3wt％的光引发剂I-184光固化成型，对制得的漆膜进行取样检测，按GB/T 1720—1979检测涂层的附着力；采用BYK微型光泽仪测试涂层的光泽度；按GB/T 6739-2006测试涂层的铅笔硬度；采用BYK摆杆硬度仪按ASTM D4366测定涂层的摆杆硬度。其检测性能结果如表6所示。
表6 不同氨基环氧丙烯酸酯涂料薄膜的性能指标
树脂 生物基含量 光泽度 附着力 铅笔硬度 摆杆硬度 Tg(℃)
实施例9 76.7％ 109±3 1 4H 162±2 77.9
对照1 70.7％ 111±1.3 0 4H 68±1 69
对照2 0％ —— 0-1 6-7H —— ——
对照1是申请号201610010125.1中的含三嗪环的光固化树脂，按GB/T 1720—1979检测涂层的附着力；采用BYK微型光泽仪测试涂层的光泽度；按GB/T 6739-2006测试涂层的铅笔硬度；采用BYK摆杆硬度仪按ASTM D4366测定涂层的摆杆硬度。其因为缺少刚性基团摆杆硬度与Tg明显低于本实例中所获得的醚化生物基氨基环氧丙烯酸酯。
对照2是“应明友.新型光敏性预聚物的合成及其在油墨中的应用[D].江南大学,2008.”里3.3.5的石油基氨基丙烯酸树脂，使用QHQ-A型涂膜铅笔划痕硬度仪(天津市材料试验机厂)测试其涂膜硬度，使用QFZ-Ⅱ型涂膜附着力试验仪(天津市科联材料试验机厂)测试其涂层附着力。由于其树脂原料均来源于石油基，树脂生物基含量为0％，可生物降解性差，其硬度过高(6-7H)导致其固化膜脆性大，缺乏柔韧性难以作为基体树脂使用，严重限制其应用领域与大规模推广。本实例中所获得的醚化生物基氨基环氧丙烯酸酯相对于对照2中氨基丙烯酸酯具有良好的可生物降解性，绿色环保，且涂层性能更加均衡优异。
虽然本发明已以较佳实施例公开如上，但其并非用以限定本发明，任何熟悉此技术的人， 在不脱离本发明的精神和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权利要求书所界定的为准。

Claims (15)

  1. 一种醚化生物基树脂，其结构与(a)～(c)中的任意一个化合物一致：
    (a)使用羟乙基腰果酚醚对氨基树脂进行醚化改性反应得到的化合物；
    (b)在(a)所得化合物的基础上，使与羟乙基腰果酚醚对应的脂肪链上的至少1个不饱和双键发生环氧化反应而得到的化合物；
    (c)在(b)所得化合物的基础上，使环氧化位点发生开环酯化反应而得到的化合物；
    (d)在(a)、(b)或(c)所得化合物的基础上进一步发生基团取代而得到的与对应(a)、(b)或(c)所得化合物性能接近的化合物。
  2. 根据权利要求1所述的醚化生物基树脂，其特征在于，所述(c)中环氧化位点是与丙烯酸或者甲基丙烯酸发生开环酯化反应。
  3. 根据权利要求1所述的醚化生物基树脂，其特征在于，所述氨基树脂为含有氨基的化合物与醛类经缩聚制得预聚体，再经碳链长度为1～9的烷醇进行醚化处理得到的油溶性化合物。
  4. 根据权利要求3所述的醚化生物基树脂，其特征在于，所述含有氨基的化合物包括三聚氰胺、尿素、苯代三聚氰胺中的任意一种。
  5. 根据权利要求1～4任一所述的醚化生物基树脂，其特征在于，氨基树脂的份数为10～15重量份、羟乙基腰果酚醚30～120重量份。
  6. 根据权利要求1～4任一所述的醚化生物基树脂，其特征在于，所述醚化生物基树脂的结构式如式(1)所示：
    Figure PCTCN2018072054-appb-100001
    其中，R为以下任意一种：
    Figure PCTCN2018072054-appb-100002
  7. 权利要求1～4任一所述的醚化生物基树脂的制备方法，其特征在于，所述醚化改性反应，包括：
    (1)将氨基树脂、羟乙基腰果酚醚、催化剂和反应溶剂，按照一定比例混合，升温至90～125℃；
    (2)反应一段时间，使反应体系中生成的小分子醇类与反应溶剂共沸，从而脱出醇类小分子；
    (3)继续反应一段时间后冷却、脱除反应溶剂；
    (4)对上一步所得产物进行洗涤，除去催化剂和未反应的原料，脱除溶剂、干燥。
  8. 根据权利要求7所述的的制备方法，其特征在于，所述醚化改性反应，还包括步骤(5)和步骤(6)，其中，
    步骤(5)将上一步所得产物与单羟基醚、催化剂混合，升温至90～130℃；
    步骤(6)反应一段时间后，降温、除去未反应的单羟基醚，干燥，得产品。
  9. 根据权利要求7所述的的制备方法，其特征在于，所述醚化改性反应中，氨基树脂10～15重量份、羟乙基腰果酚醚30-120重量份、催化剂0.1～0.3重量份。
  10. 根据权利要求8所述的的制备方法，其特征在于，所述醚化改性反应中，氨基树脂10～15重量份、羟乙基腰果酚醚30-120重量份、催化剂0.1～0.3重量份、单羟基醚20～50重量份。
  11. 根据权利要求7所述的的制备方法，其特征在于，所述步骤(1)催化剂为对甲苯磺酸、苯乙烯磺酸、氨基磺酸、苯甲酸、苯乙酸、邻苯二甲酸、对苯二甲酸、草酸或磷酸中的任意一种或多种。
  12. 权利要求1-6任一所述的醚化生物基树脂的应用，其特征在于，所述应用包括用于涂料工业、皮革鞣剂、胶黏剂、阻燃材料、3D打印等领域。
  13. 权利要求1-6任一所述的醚化生物基树脂的应用，其特征在于，所述应用包括作为涂料、交联剂、胶粘剂、层压材料、3D打印或模塑料用树脂，或者织物、纸张、皮革等的处理剂。
  14. 一种涂料，其特征在于，包含权利要求1-6任一所述的醚化生物基树脂。
  15. 一种3D打印材料或阻燃材料，其特征在于，所述3D打印材料或阻燃材料的原料包括权利要求1-6任一所述的醚化生物基树脂。
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