CN106832186A - One kind mixing diisocyanate type urethane and preparation method thereof - Google Patents

One kind mixing diisocyanate type urethane and preparation method thereof Download PDF

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Publication number
CN106832186A
CN106832186A CN201710009906.3A CN201710009906A CN106832186A CN 106832186 A CN106832186 A CN 106832186A CN 201710009906 A CN201710009906 A CN 201710009906A CN 106832186 A CN106832186 A CN 106832186A
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diisocyanate
reaction
mixing
type urethane
dmf
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任龙芳
耿瑾
强涛涛
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group

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  • Chemical & Material Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention relates to polymer applied technical field, and in particular to the mixing diisocyanate type urethane for preparing a kind of color inhibition as raw material with partially aromatic isocyanates and aliphatic isocyanates.The preparation method includes five big steps, selection aromatic diisocyanate and aliphatic diisocyanate are mixed with polyurethane with different molal weight ratios, by using two or more isocyanates, the activity of reaction is different, change the state of molecular structure, reduce the unsaturated double-bond quantity that phenyl ring has, polymer is reduced because there is unsaturated double-bond, influenceed by extraneous factor and caused being inclined to for polymer xanthochromia, the cost of simple use aliphatic isocyanates has been saved to a certain extent, while reaching the requirement of technical grade anti-yellowing property.Mix diisocyanate type urethane obtained in of the invention on the premise of the good anti-yellowing property of polyurethane film is ensured, while improve the bonding effect of product and the scope of application.

Description

One kind mixing diisocyanate type urethane and preparation method thereof
Technical field
The present invention relates to polymer applied technical field, and in particular to different with partially aromatic isocyanates and aliphatic Cyanate is the mixing diisocyanate type urethane that raw material prepare a kind of color inhibition.
Background technology
Polyurethane is to form carbamate by polyisocyanates and polyol reaction, is important point of petrochemicals Branch.Due to containing highly polar carbamate groups, insoluble in non-polar group, with good oil resistivity, toughness, wearability, Resistance to ag(e)ing and cohesive.Therefore polyurethane material with the forms such as emulsion, resin, elastomer be widely used in transport, household electrical appliances, The field such as machinery, building, light textile, shoemaking, athletic equipment and place, agricultural, national defence, is a kind of multi-functional polymeric material.
Solvent-borne type PU resins are used in country's synthetic leather production process at present as basic unit and the base stock of surface layer, But conventional TDI types and MDI type polyurethanes uses the photooxidation resistance phenomenons such as easy yellowing, cracking, mechanical performance decline out of doors. Under normal circumstances, polyurethane is by light irradiation（Natural light, ultraviolet light etc.）The degradation with aging that can cause afterwards.The absorption of polyurethane Wavelength is general between 209 ~ 400 nm, and the molecular link after the light of the certain wavelength of absorption in material occurs fracture or crosslinking is released CO2With CO gases, the physical and mechanical properties decline of material is ultimately resulted in, while can also generate coloured groups, cause the face of material Color is deepened.This is that its structure easily changes because partially aromatic polyurethane is under light illumination especially under the irradiation of ultraviolet light And discoloration is produced, properties of product are influenceed, therefore solve the problems, such as the development of the xanthochromia to Polyurethane Industry of partially aromatic polyurethane It is significant.
Because polyurethane is widely applied performance, in order to improve yellowing resistance energy, mechanical strength, the stability of polyurethane On the one hand it is modified by polyurethane Deng, researcher, its yellowing resistance is improved, on the other hand by preferably suitable Anti-yellowing agent come effectively slow down its xanthochromia reaction.
The content of the invention
Goal of the invention：Regarding to the issue above, the invention provides a kind of preparation side for mixing diisocyanate type urethane Method, is a kind of solvent borne polyurethane of Material synthesis with aromatic diisocyanate and aliphatic diisocyanate, and it can be extensive It is applied to the fields such as coating, adhesive, construction material, automobile, weaving.
To achieve these goals, the technical solution adopted by the present invention is：
A kind of preparation method for mixing diisocyanate type urethane, comprises the following steps：
(1) polyalcohol is added equipped with thermometer, condensing unit, split type three mouthfuls of reaction flasks of mechanical agitator, 100 3 ~ 4h is dehydrated under ~ 105 DEG C of vacuum conditions, 55 ~ 65 DEG C are cooled to；
(2) it is 9-1 by mol ratio:1-9's
Aromatic diisocyanate mixes with aliphatic diisocyanate, the amount of mixing diisocyanate and polyalcoholn(-NCO):n(- OH) is 1:1, mixing diisocyanate is dissolved in dried DMF（DMF）In, it is configured to quality Concentration is the DMF solution of 30-50%, is dropped in the system of step (1), and 1 ~ 1.5h is stirred at being 20 ~ 25 DEG C in temperature；
(3) to the catalyst dibutyltin dilaurylate (DBTDL) that 0.01% ~ 0.07% is added in the reaction system of step (2), urge In terms of the gross mass for mixing diisocyanate and polyalcohol, be heated to 65 ~ 70 DEG C carries out prepolymerization reaction to the consumption of agent, protects 2 ~ 3h of temperature reaction；Obtain base polyurethane prepolymer for use as；
(4) will be with step (2) identical type and the mixing diisocyanate and 1,4- butanediols of mixed in molar ration(-NCO):n(- OH it is) 1:1 is dissolved in dried N,N-dimethylformamide（DMF）In, it is configured to the DMF that mass concentration is 30-50% molten Liquid, is dropped in the base polyurethane prepolymer for use as system in step (3), and chain extending reaction, insulation reaction are carried out at being 40 ~ 45 DEG C in temperature 1~1.5h；It is warming up to 65 ~ 70 DEG C, 2 ~ 3h of insulation reaction；
(5) absolute ethyl alcohol is added in the product that forwardly step is obtained（n(-NCO):n(- OH) is according to 1:1）, at 80 ~ 85 DEG C Carry out end capping reaction, 1 ~ 2h of insulation reaction；Room temperature is cooled to, a kind of mixing diisocyanate type urethane is obtained.
The addition of mixing diisocyanate and the addition for mixing diisocyanate in step (4) in the step (2) Number ratio be 15 parts：80 parts.
Above-mentioned steps（4）With（5）Between the step of also have a regulation system viscosity, by a small amount of repeatedly by 5 parts of mixing Diisocyanate is dissolved in dried N,N-dimethylformamide（DMF）In, it is added dropwise in the system of step (4) to adjust body It is viscosity, the reaction time is 1 ~ 1.5h, and reaction temperature is controlled at 65 ~ 70 DEG C.
In the step of regulation system viscosity, mixing diisocyanate is dissolved in dried DMF （DMF）In, 50% DMF solution is configured to, it is added dropwise in the system of step (4) and carrys out regulation system viscosity, can finally obtain difference Polyurethane finished product under viscosity.
Polyalcohol is polyneopentyl glycol adipate, polycaprolactone, polymethylene carbonic ester, poly- in the step (1) Tetrahydrofuran ether glycol or polyadipate-BDO ester, selected polyalcohol polarity are stronger, and prepared polyurethane is resistance to Hot, water resistance and mechanical property are preferable.
Mixing diisocyanate in the step (2) is toluene di-isocyanate(TDI) (TDI)/IPDI (IPDI), methyl diphenylene diisocyanate (MDI)/hexamethylene diisocyanate (HDI), PPDI (PPDI)/dicyclohexyl methyl hydride diisocyanate (HMDI).
Added in the step (2)n(- OH) is slightly excessive, to control the carrying out of prepolymerization reaction；Add in the step (3) Entern(- NCO) is slightly excessive, to ensure persistently carrying out for chain extending reaction.
Mix the poly- ammonia of diisocyanate type by obtained in the described preparation method for mixing diisocyanate type urethane Ester.
Compared with prior art, it is an advantage of the invention that：
1. present invention selection aromatic diisocyanate and aliphatic diisocyanate are mixed with poly- with different molal weight ratios Urethane, by using two or more isocyanates, the activity of reaction is different, changes the state of molecular structure, reduces benzene The unsaturated double-bond quantity that ring has, reduces polymer because there is unsaturated double-bond, is influenceed by extraneous factor and causes polymer The tendency of xanthochromia, has saved the cost of simple use aliphatic isocyanates to a certain extent, while reaching the resistance to Huang of technical grade Become the requirement of performance；
2. the invention provides a kind of preparation method for mixing diisocyanate type urethane, obtained mixing diisocyanate type Polyurethane is on the premise of polyurethane film good anti-yellowing property is ensured, while improve bonding effect and the application of product Scope.
Brief description of the drawings
Fig. 1 is the synthetic route chart of mixing diisocyanate type urethane preparation method of the present invention；
Fig. 2 is isofoer diisocyanate（IPDI）With methyl diphenylene diisocyanate（MDI）Mol ratio is 7:3、3:7 Hes 0:10 polyurethane film infrared spectrogram, wherein a represents that mol ratio is 7:Polyurethane film prepared by 3, b represents that mol ratio is 3: Polyurethane film obtained by 7, c mol ratios are 0:Polyurethane film obtained by 10.
Fig. 3 is isofoer diisocyanate（IPDI）With methyl diphenylene diisocyanate（MDI）Mol ratio is 7:3、 3:7 and 0:Ultraviolet permeability curve map before and after 10 polyurethane film illumination.Wherein（a）Polyurethane film is ultraviolet before expression illumination Cross rate,（a）The ultraviolet permeability of polyurethane film after expression illumination.
Specific embodiment
The synthetic route of mixing diisocyanate type urethane preparation method of the present invention is as shown in Figure 1.
A kind of preparation method for mixing diisocyanate type urethane, comprises the following steps：
(1) polyalcohol is added equipped with thermometer, condensing unit, split type three mouthfuls of reaction flasks of mechanical agitator, 100 3 ~ 4h is dehydrated under ~ 105 DEG C of vacuum conditions, 55 ~ 65 DEG C are cooled to；
(2) it is 9-1 by mol ratio:1-9's
Aromatic diisocyanate mixes with aliphatic diisocyanate, the amount of mixing diisocyanate and polyalcoholn(-NCO):n(- OH) is 1:1, mixing diisocyanate is dissolved in dried DMF（DMF）In, it is configured to quality Concentration is the DMF solution of 30-50%, is dropped in the system of step (1), and 1 ~ 1.5h is stirred at being 20 ~ 25 DEG C in temperature；
(3) to the catalyst dibutyltin dilaurylate (DBTDL) that 0.01% ~ 0.07% is added in the reaction system of step (2), urge In terms of the gross mass for mixing diisocyanate and polyalcohol, be heated to 65 ~ 70 DEG C carries out prepolymerization reaction to the consumption of agent, protects 2 ~ 3h of temperature reaction；Obtain base polyurethane prepolymer for use as；
(4) will be with step (2) identical type and the mixing diisocyanate and 1,4- butanediols of mixed in molar ration(-NCO):n(- OH it is) 1:1 is dissolved in dried N,N-dimethylformamide（DMF）In, it is configured to the DMF that mass concentration is 30-50% molten Liquid, is dropped in the base polyurethane prepolymer for use as system in step (3), and chain extending reaction, insulation reaction are carried out at being 40 ~ 45 DEG C in temperature 1~1.5h；It is warming up to 65 ~ 70 DEG C, 2 ~ 3h of insulation reaction；
(5) absolute ethyl alcohol is added in the product that forwardly step is obtained（n(-NCO):n(- OH) is according to 1:1）, at 80 ~ 85 DEG C Carry out end capping reaction, 1 ~ 2h of insulation reaction；Room temperature is cooled to, a kind of mixing diisocyanate type urethane is obtained.
The addition of mixing diisocyanate and the addition for mixing diisocyanate in step (4) in the step (2) Number ratio be 15 parts：80 parts.
Above-mentioned steps（4）With（5）Between the step of also have a regulation system viscosity, by a small amount of repeatedly by 5 parts of mixing Diisocyanate is dissolved in dried N,N-dimethylformamide（DMF）In, it is added dropwise in the system of step (4) to adjust body It is viscosity, the reaction time is 1 ~ 1.5h, and reaction temperature is controlled at 65 ~ 70 DEG C.
In the step of regulation system viscosity, mixing diisocyanate is dissolved in dried DMF （DMF）In, 50% DMF solution is configured to, it is added dropwise in the system of step (4) and carrys out regulation system viscosity, can finally obtain difference Polyurethane finished product under viscosity.
Polyalcohol is polyneopentyl glycol adipate, polycaprolactone, polymethylene carbonic ester, poly- in the step (1) Tetrahydrofuran ether glycol or polyadipate-BDO ester, selected polyalcohol polarity are stronger, and prepared polyurethane is resistance to Hot, water resistance and mechanical property are preferable.
Mixing diisocyanate in the step (2) is toluene di-isocyanate(TDI) (TDI)/IPDI (IPDI), methyl diphenylene diisocyanate (MDI)/hexamethylene diisocyanate (HDI), PPDI (PPDI)/dicyclohexyl methyl hydride diisocyanate (HMDI).
Added in the step (2)n(- OH) is slightly excessive, to control the carrying out of prepolymerization reaction；Add in the step (3) Entern(- NCO) is slightly excessive, to ensure persistently carrying out for chain extending reaction.
Mix diisocyanate type urethane obtained in the preparation method of diisocyanate type urethane by mixing.
The present invention is described in further details with reference to several specific embodiments.
Embodiment 1
One kind mixing diisocyanate type urethane preparation method, during preparation, takes equipped with reflux condensing tube, mechanical agitation rod, temperature Split type three mouthfuls of reaction flasks of meter are spent, preparation is followed the steps below：
(1) by 0.01mol PTMGs 2000 add equipped with thermometer, condensing unit, mechanical agitator split In three mouthfuls of reaction flasks of formula, 4h is dehydrated under 100 vacuum conditions, is cooled to 60 DEG C；
(2) by isofoer diisocyanate（IPDI）With methyl diphenylene diisocyanate（MDI）Mol ratio is 1:1 0.0072mol mixing diisocyanate is dissolved in dried N,N-dimethylformamide（DMF）In, being configured to mass concentration is 50% DMF solution, is dropped in the system of step (1), and 1h is stirred at being 25 DEG C in temperature；
(3) to the catalyst dibutyltin dilaurylate (DBTDL) that 0.03% is added in the reaction system of step (2), heat temperature raising Prepolymerization reaction, insulation reaction 2h are carried out to 70 DEG C；Obtain base polyurethane prepolymer for use as；
(4) by isofoer diisocyanate（IPDI）With methyl diphenylene diisocyanate（MDI）Mol ratio is 1:1 0.08mol mixing diisocyanate, 0.076mol 1,4- butanediols dissolving N,N-dimethylformamide after the drying（DMF） In, the DMF solution that mass concentration is 50% is configured to, drop in the system of base polyurethane prepolymer for use as in step (3), be in temperature Chain extending reaction, insulation reaction 1.5h are carried out at 45 DEG C；It is warming up to 70 DEG C, insulation reaction 2h；
(5) by a small amount of repeatedly successively by the mixing diisocyanate of 0.002mol, 0.002mol, 0.001mol, 0.001mol It is dissolved in dried N,N-dimethylformamide（DMF）In, 50% DMF solution is configured to, it is added dropwise to the system of step (4) In carry out regulation system viscosity, react 1h at 70 DEG C.
(6) to adding absolute ethyl alcohol 0.0044mol in step (5), in carrying out end capping reaction, insulation reaction 1h at 80 DEG C； Room temperature is cooled to, a kind of IPDI/MDI mixing diisocyanate type urethane is obtained.
Embodiment 2
One kind mixing diisocyanate type urethane preparation method, during preparation, takes equipped with reflux condensing tube, mechanical agitation rod, temperature Split type three mouthfuls of reaction flasks of meter are spent, preparation is followed the steps below：
(1) by 0.02mol PTMGs 2000 add equipped with thermometer, condensing unit, mechanical agitator split In three mouthfuls of reaction flasks of formula, 4h is dehydrated under 100 vacuum conditions, is cooled to 60 DEG C；
(2) it is 3 by toluene di-isocyanate(TDI) (TDI)/hexamethylene diisocyanate (HDI) mol ratio:7 0.0156mol is mixed Close diisocyanate and be dissolved in dried N,N-dimethylformamide（DMF）In, it is configured to the DMF that mass concentration is 30% molten Liquid, is dropped in the system of step (1), and 1.5h is stirred at being 20 DEG C in temperature；
(3) to the catalyst dibutyltin dilaurylate (DBTDL) that 0.06% is added in the reaction system of step (2), heat temperature raising Prepolymerization reaction, insulation reaction 2h are carried out to 75 DEG C；Obtain base polyurethane prepolymer for use as；
(4) toluene di-isocyanate(TDI) (TDI)/hexamethylene diisocyanate (HDI) mol ratio is 3:7 0.08mol mixing two Isocyanates, 0.072mol 1,4- butanediols dissolving N,N-dimethylformamide after the drying（DMF）In, it is configured to quality Concentration is 50% DMF solution, is dropped in the system of base polyurethane prepolymer for use as in step (3), and chain extension is carried out at being 50 DEG C in temperature Reaction, insulation reaction 1h；It is warming up to 65 DEG C, insulation reaction 2h；
(5) by a small amount of repeatedly successively by the mixing diisocyanate of 0.002mol, 0.002mol, 0.001mol, 0.001mol It is dissolved in dried N,N-dimethylformamide（DMF）In, 50% DMF solution is configured to, it is added dropwise to the system of step (4) In carry out regulation system viscosity, react 1.5h at 65 DEG C.
(6) to adding absolute ethyl alcohol 0.0096mol in step (5), in carrying out end capping reaction, insulation reaction at 85 DEG C 1.5h；Room temperature is cooled to, a kind of TDI/HDI mixing diisocyanate type urethane is obtained.
Embodiment 3
One kind mixing diisocyanate type urethane preparation method, during preparation, takes equipped with reflux condensing tube, mechanical agitation rod, temperature Split type three mouthfuls of reaction flasks of meter are spent, preparation is followed the steps below：
(1) 0.015mol polyadipate -1,4- butanediol esters 2000 are added equipped with thermometer, condensing unit, mechanical agitator Split type three mouthfuls of reaction flasks in, be dehydrated 3h under 105 vacuum conditions, be cooled to 55 DEG C；
(2) by isofoer diisocyanate（IPDI）With methyl diphenylene diisocyanate（MDI）Mol ratio is 7:3 0.012mol mixing diisocyanate is dissolved in dried N,N-dimethylformamide（DMF）In, being configured to mass concentration is 50% DMF solution, is dropped in the system of step (1), and 1.5h is stirred at being 25 DEG C in temperature；
(3) to the catalyst dibutyltin dilaurylate (DBTDL) that 0.05% is added in the reaction system of step (2), heat temperature raising Prepolymerization reaction, insulation reaction 2.5h are carried out to 65 DEG C；Obtain base polyurethane prepolymer for use as；
(4) by isofoer diisocyanate（IPDI）With methyl diphenylene diisocyanate（MDI）Mol ratio is 7:3 0.075mol mixing diisocyanate, 0.06mol 1,4- butanediols dissolving N,N-dimethylformamide after the drying（DMF） In, 35% DMF solution is configured to, drop in the system of base polyurethane prepolymer for use as in step (3), carried out at being 40 DEG C in temperature Chain extending reaction, insulation reaction 1.5h；It is warming up to 65 DEG C, insulation reaction 3h；
(5) to adding absolute ethyl alcohol 0.012mol in step (4), in carrying out end capping reaction, insulation reaction 1.5h at 85 DEG C；Cooling To room temperature, a kind of IPDI/MDI mixing diisocyanate type urethane is obtained.
Fig. 2 is respectively isofoer diisocyanate（IPDI）With methyl diphenylene diisocyanate（MDI）Mol ratio is 7:3、3:7 and 0:10 polyurethane film infrared spectrogram, wherein a represents that mol ratio is 7:Polyurethane film prepared by 3, b is represented Mol ratio is 3:Polyurethane film obtained by 7, c mol ratios are 0:Polyurethane film obtained by 10.As seen from Figure 2, exist 3250~3500cm-1The peak for locating appearance is the cis NH stretching vibrations of NHCO, 1700 ~ 1750cm-1Neighbouring peak belongs to acyl The characteristic absorption peak of amine I generation C=O, 1600 ~ 1615cm-1For phenyl ring C=C frame expansions vibrate, 1520 ~ 1560cm-1It is acid amides II For the absworption peak of N-H deformation vibrations.Mix the film spectrogram prepared by isocyanates under contrast different mol ratio to find, three kinds of spectrums The peak shape of figure is similar, but has some differences in the absorption intensity at some peaks.With the increase of aromatic isocyanate content, 1600cm-1Neighbouring absorption peak strength gradually increases, and shows that the content of phenyl ring in polyurethane structural is stepped up, its yellowing resistance Gradually reduce.
Fig. 3 is isofoer diisocyanate（IPDI）With methyl diphenylene diisocyanate（MDI）Mol ratio is 7:3、 3:7 and 0:Ultraviolet permeability curve map before and after 10 polyurethane film illumination.Wherein Fig. 3（a）The purple of polyurethane film before expression illumination Outer transmitance, Fig. 3（b）The ultraviolet permeability of polyurethane film after expression illumination.Comparison diagram 3（a）、（b）Two figures are it can be found that light Polyurethane film ultraviolet permeability according to after is substantially reduced, and this is the amine ester bond in structure in the presence of ultraviolet because of polyurethane film Easily decompose, the methylene that oxidation generation quinones chromophoric group is connected with phenyl ring is easily oxidized to and brings it about xanthochromia, thus it is ultraviolet Transmitance reduction.And contrast the polyurethane film of different mixing isocyanates mol ratios before and after illumination, it is found that it is different with mixing Methyl diphenylene diisocyanate in cyanate（MDI）The increase of amount, ultraviolet permeability is reduced successively, and this is due to increasing in system Added the unsaturated double-bond quantity that phenyl ring has, so as to increase polymer because there is unsaturated double-bond, influenceed by extraneous factor and Cause the tendency of polymer xanthochromia, therefore ultraviolet permeability reduction.

Claims (8)

1. it is a kind of mix diisocyanate type urethane preparation method, it is characterised in that comprise the following steps：
(1) polyalcohol is added equipped with thermometer, condensing unit, split type three mouthfuls of reaction flasks of mechanical agitator, 100 3 ~ 4h is dehydrated under ~ 105 DEG C of vacuum conditions, 55 ~ 65 DEG C are cooled to；
(2) it is 9-1 by mol ratio:The aromatic diisocyanate of 1-9 mixes with aliphatic diisocyanate, mixes two isocyanic acids The amount of ester and polyalcoholn(-NCO):n(- OH) is 1:1, mixing diisocyanate is dissolved in dried N, N- dimethyl methyls Acid amides（DMF）In, be configured to the DMF solution that mass concentration is 30-50%, in dropping to the system of step (1), temperature be 20 ~ 1 ~ 1.5h is stirred at 25 DEG C；
(3) to the catalyst dibutyltin dilaurylate (DBTDL) that 0.01% ~ 0.07% is added in the reaction system of step (2), urge In terms of the gross mass for mixing diisocyanate and polyalcohol, be heated to 65 ~ 70 DEG C carries out prepolymerization reaction to the consumption of agent, protects 2 ~ 3h of temperature reaction；Obtain base polyurethane prepolymer for use as；
(4) will be with step (2) identical type and the mixing diisocyanate and 1,4- butanediols of mixed in molar ration(-NCO):n(- OH it is) 1:1 is dissolved in dried N,N-dimethylformamide（DMF）In, it is configured to the DMF that mass concentration is 30-50% molten Liquid, is dropped in the base polyurethane prepolymer for use as system in step (3), and chain extending reaction, insulation reaction are carried out at being 40 ~ 45 DEG C in temperature 1~1.5h；It is warming up to 65 ~ 70 DEG C, 2 ~ 3h of insulation reaction；
(5) absolute ethyl alcohol is added in the product that forwardly step is obtained（n(-NCO):n(- OH) is according to 1:1）, at 80 ~ 85 DEG C Carry out end capping reaction, 1 ~ 2h of insulation reaction；Room temperature is cooled to, a kind of mixing diisocyanate type urethane is obtained.
2. it is according to claim 1 mixing diisocyanate type urethane preparation method, it is characterised in that：The step (2) addition of mixing diisocyanate is 15 with the number ratio of the addition for mixing diisocyanate in step (4) in Part：80 parts.
3. it is according to claim 1 and 2 mixing diisocyanate type urethane preparation method, it is characterised in that：It is above-mentioned Step（4）With（5）Between the step of also have a regulation system viscosity, by a small amount of repeatedly that 5 parts of mixing diisocyanate are molten Solution N,N-dimethylformamide after the drying（DMF）In, it is added dropwise in the system of step (4) and carrys out regulation system viscosity, react Time is 1 ~ 1.5h, and reaction temperature is controlled at 65 ~ 70 DEG C.
4. it is according to claim 3 mixing diisocyanate type urethane preparation method, it is characterised in that：The regulation In the step of system viscosity, mixing diisocyanate is dissolved in dried DMF（DMF）In, it is configured to 50% DMF solution, is added dropwise in the system of step (4) and carrys out regulation system viscosity, can finally obtain the polyurethane under different viscositys Finished product.
5. it is according to claim 4 mixing diisocyanate type urethane preparation method, it is characterised in that：The step (1) in polyalcohol be polyneopentyl glycol adipate, polycaprolactone, polymethylene carbonic ester, PTMG or Polyadipate-BDO ester, selected polyalcohol polarity is stronger, prepared polyurethane heat resistant, water resistance and Mechanical property is preferable.
6. it is according to claim 5 mixing diisocyanate type urethane preparation method, it is characterised in that：The step (2) the mixing diisocyanate in is toluene di-isocyanate(TDI) (TDI)/IPDI (IPDI), diphenylmethyl Alkane diisocyanate (MDI)/hexamethylene diisocyanate (HDI), PPDI (PPDI)/dicyclohexyl methyl hydride two Isocyanates (HMDI).
7. it is according to claim 6 mixing diisocyanate type urethane preparation method, it is characterised in that：The step (2) added inn(- OH) is slightly excessive, to control the carrying out of prepolymerization reaction；Added in the step (3)n(- NCO) slightly mistake Amount, to ensure persistently carrying out for chain extending reaction.
8. the preparation method of mixing diisocyanate type urethane according to claim 1 is obtained mixes diisocyanate Type polyurethane.
CN201710009906.3A 2017-01-06 2017-01-06 One kind mixing diisocyanate type urethane and preparation method thereof Pending CN106832186A (en)

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CN110982471A (en) * 2019-12-05 2020-04-10 浙江工业大学之江学院 Washable polyurethane adhesive composition and preparation method thereof
CN114057991A (en) * 2021-12-02 2022-02-18 万华化学集团股份有限公司 Fast-curing polyisocyanate composition and preparation method and application thereof

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CN110982471A (en) * 2019-12-05 2020-04-10 浙江工业大学之江学院 Washable polyurethane adhesive composition and preparation method thereof
CN114057991A (en) * 2021-12-02 2022-02-18 万华化学集团股份有限公司 Fast-curing polyisocyanate composition and preparation method and application thereof
CN114057991B (en) * 2021-12-02 2023-03-03 万华化学集团股份有限公司 Fast-curing polyisocyanate composition and preparation method and application thereof

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Application publication date: 20170613