CN106519163A - Method for preparing cross-linked polyurethane film - Google Patents

Method for preparing cross-linked polyurethane film Download PDF

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Publication number
CN106519163A
CN106519163A CN201611014993.3A CN201611014993A CN106519163A CN 106519163 A CN106519163 A CN 106519163A CN 201611014993 A CN201611014993 A CN 201611014993A CN 106519163 A CN106519163 A CN 106519163A
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constant pressure
film
pressure funnel
dmpa
thpdms
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王耀斌
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Shaanxi Shengmai Petroleum Co Ltd
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Shaanxi Shengmai Petroleum Co Ltd
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Priority to CN201611014993.3A priority Critical patent/CN106519163A/en
Publication of CN106519163A publication Critical patent/CN106519163A/en
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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
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/61—Polysiloxanes
    • 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
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to the technical field of functional materials, in particular to a method for preparing a cross-linked polyurethane film. The method for preparing the cross-linked polyurethane film includes the following steps that (1) organosilicone-modification multiple-arm-type waterborne polyurethane resin preparing; (2) curing film preparing. According to the method, as THPDMS is added, the heat stability of an adhesive film can be improved to a certain degree; meanwhile, as soft-and-hard-phase micro separation of the surface of a TWPU film appears, and micro-phase separation is enhanced along with increasing of the THPDMS content, the particle size of emulsion is gradually increased, a water contact angle is increased, and water absorption rate of the adhesive film is reduced; the relatively-good tensile strength and the relatively-good breaking elongation are 7.25 MPa and 250% respectively.

Description

The preparation method of cross-linked polyurethane film
Technical field
The present invention relates to technical field of function materials, and in particular to a kind of preparation method of cross-linked polyurethane film.
Background technology
Photocuring aqueous polyurethane with its exclusive energy-saving and environmental protection, curing rate it is fast, etc. excellent performance be subject to the country The concern of outer Many researchers.But some performances of aqueous polyurethane are not met by being actually needed, such as hardness, resistance to water, heat Stability, surface property and tensile strength etc., thus, limit the range of application of film. so, aqueous polyurethane is modified Just become inexorable trend.
End hydroxy polyether modified silicon oil (THPDMS) has good hydrophobicity, resistance to water, thermostability, insulating properties, flexible The advantages of property and lower glass transition temperatures, makes it have the prospect of being widely applied.PDMS segments are incorporated into into polyurethane segment The organic silicon modified aqueous polyurethane of middle formation can have the property of polyurethane and organosilicon simultaneously.It is excellent in order to obtain which Physicochemical property, with terminal hydroxy group organosilicon (PDMS) as soft section modified aqueous polyurethane, research finds that PDMS can improve glued membrane Heat stability, resistance to water and surface hydrophobic.Herein with the poly- ammonia of aqueouss that modified HDI trimers (HDT) of THPDMS are core Ester, by increasing capacitance it is possible to increase the active group of photocuring aqueous polyurethane, improves photocuring activity and can largely lift water Property the mechanical strength of polyurethane, water resistance, hardness and heat resistance, improve the range of application of aqueous polyurethane.
The content of the invention
It is contemplated that proposing a kind of preparation method of cross-linked polyurethane film.
Technical program of the present invention lies in：
The preparation method of cross-linked polyurethane film, comprises the steps：
（1）The preparation of organic-silicon-modified many arm type waterborne polyurethane resins
Weigh a certain amount of IPDI and DBTDL and add doing equipped with agitator, condensing tube, constant pressure funnel and nitrogen conduit In dry four-hole boiling flask, it is stirred at room temperature uniformly, is passed through nitrogen protection, is progressively warming up to 45 DEG C, with constant pressure funnel control drop speed 2 ~ 3s/ drops dropwise the PCDL sums of 0.5 times of IPDI molal quantity of Deca THPDMS reaction 2h, per 0.5h sampling titration system in Free-NCO content, when dissociate in system-NCO content reach theoretical value after, stopped reaction；Product Labeling is IPDI- PCDL-THPDMS；
DBTDL and DMPA are added and is dried four-hole boiling flask equipped with agitator, condensing tube, constant pressure funnel and nitrogen conduit In, it is stirred at room temperature uniformly, is passed through nitrogen protection, is progressively warming up to 50 DEG C, then with constant pressure funnel control drop speed in 2 ~ 3s/ The HDT of dropwise 1/3 mol times DMPA of Deca is dripped, 2h is reacted, free-NCO contents in every 0.5 h samplings titration system, After theoretical value is reached, product is designated as HDT-DMPA；
Temperature rises to 75 DEG C, with constant pressure funnel control drop speed in 2 ~ 3s/ drops dropwise Deca HDT-DMPA, addition it is appropriate third Ketone adjusts reaction viscosity, reacts 3h ,-NCO the contents dissociated in sampling titration system per 0.5h, after theoretical value is reached, uses Constant pressure funnel control drop speed obtains final product branch polyurethane in 2 ~ 3s/ drops dropwise a certain amount of HEA of Deca, will be obtained Resin is cooled to 40 DEG C, adds the TEA neutralization reaction 1h of the identical molal quantitys of DMPA under high velocity agitation, and add water 1 h of emulsifying, quiet Acetone is removed with Rotary Evaporators after putting froth breaking organic-silicon-modified many arm type aqueous polyurethanes are obtained；
（2）The preparation of cured film
Weigh polyaminoester emulsion, add the water-soluble photoinitiator of gross mass 5%, add a certain amount of levelling agent, coalescents, Defoamer, after being stirred at room temperature uniformly, solution is poured in Teflon mold, and room temperature places 24 h, and 60 DEG C of baking ovens dry 2h, then will Film carries out solidification 40s and obtains cross-linked polyurethane film in being put into uviol lamp photo solidification machine.
Described IPDI is isoflurane chalcone diisocyanate, and DBTDL is dibutyl tin laurate, and PCDL is poly- carbonic acid Ester dihydroxylic alcohols, THPDMS are end hydroxy polyether modified silicon oil.
The method have technical effect that：
The addition of THPDMS of the present invention can improve the heat stability of glued membrane to a certain extent, simultaneously as TWPU films surface Occur the biphase differential of soft or hard from, and as the increases microphase-separated enhancing of THPDMS contents causes the particle diameter of emulsion gradually to increase, Water contact angle increase, glued membrane water absorption rate are reduced, have relatively good tensile strength and elongation at break be respectively 7.25MPa, 250%.
Specific embodiment
The preparation method of cross-linked polyurethane film, comprises the steps：
（1）The preparation of organic-silicon-modified many arm type waterborne polyurethane resins
Weigh a certain amount of IPDI and DBTDL and add doing equipped with agitator, condensing tube, constant pressure funnel and nitrogen conduit In dry four-hole boiling flask, it is stirred at room temperature uniformly, is passed through nitrogen protection, is progressively warming up to 45 DEG C, with constant pressure funnel control drop speed 2 ~ 3s/ drops dropwise the PCDL sums of 0.5 times of IPDI molal quantity of Deca THPDMS reaction 2h, per 0.5h sampling titration system in Free-NCO content, when dissociate in system-NCO content reach theoretical value after, stopped reaction；Product Labeling is IPDI- PCDL-THPDMS；
DBTDL and DMPA are added and is dried four-hole boiling flask equipped with agitator, condensing tube, constant pressure funnel and nitrogen conduit In, it is stirred at room temperature uniformly, is passed through nitrogen protection, is progressively warming up to 50 DEG C, then with constant pressure funnel control drop speed in 2 ~ 3s/ The HDT of dropwise 1/3 mol times DMPA of Deca is dripped, 2h is reacted, free-NCO contents in every 0.5 h samplings titration system, After theoretical value is reached, product is designated as HDT-DMPA temperature and rises to 75 DEG C, with constant pressure funnel control drop speed 2 ~ 3s/ drops by Drop Deca HDT-DMPA, adds appropriate acetone to adjust reaction viscosity, reacts 3h, dissociate in sampling titration system per 0.5h- NCO contents, after theoretical value is reached, with constant pressure funnel control drop speed in 2 ~ 3s/ drops dropwise a certain amount of HEA of Deca, i.e., Branch polyurethane is obtained, obtained resin is cooled to into 40 DEG C, add the TEA of the identical molal quantitys of DMPA under high velocity agitation Neutralization reaction 1h, add water 1 h of emulsifying, removes acetone with Rotary Evaporators organic-silicon-modified many arm type water are obtained after standing froth breaking Property polyurethane；
（2）The preparation of cured film
Weigh polyaminoester emulsion, add the water-soluble photoinitiator of gross mass 5%, add a certain amount of levelling agent, coalescents, Defoamer, after being stirred at room temperature uniformly, solution is poured in Teflon mold, and room temperature places 24 h, and 60 DEG C of baking ovens dry 2h, then will Film carries out solidification 40s and obtains cross-linked polyurethane film in being put into uviol lamp photo solidification machine.
Described IPDI is isoflurane chalcone diisocyanate, and DBTDL is dibutyl tin laurate, and PCDL is poly- carbonic acid Ester dihydroxylic alcohols, THPDMS are end hydroxy polyether modified silicon oil.

Claims (2)

1. the preparation method of cross-linked polyurethane film, it is characterised in that：Comprise the steps：
（1）The preparation of organic-silicon-modified many arm type waterborne polyurethane resins
Weigh a certain amount of IPDI and DBTDL and add doing equipped with agitator, condensing tube, constant pressure funnel and nitrogen conduit In dry four-hole boiling flask, it is stirred at room temperature uniformly, is passed through nitrogen protection, is progressively warming up to 45 DEG C, with constant pressure funnel control drop speed 2 ~ 3s/ drops dropwise the PCDL sums of 0.5 times of IPDI molal quantity of Deca THPDMS reaction 2h, per 0.5h sampling titration system in Free-NCO content, when dissociate in system-NCO content reach theoretical value after, stopped reaction；Product Labeling is IPDI- PCDL-THPDMS；
DBTDL and DMPA are added and is dried four-hole boiling flask equipped with agitator, condensing tube, constant pressure funnel and nitrogen conduit In, it is stirred at room temperature uniformly, is passed through nitrogen protection, is progressively warming up to 50 DEG C, then with constant pressure funnel control drop speed in 2 ~ 3s/ The HDT of dropwise 1/3 mol times DMPA of Deca is dripped, 2h is reacted, free-NCO contents in every 0.5 h samplings titration system, After theoretical value is reached, product is designated as HDT-DMPA；
Temperature rises to 75 DEG C, with constant pressure funnel control drop speed in 2 ~ 3s/ drops dropwise Deca HDT-DMPA, addition it is appropriate third Ketone adjusts reaction viscosity, reacts 3h ,-NCO the contents dissociated in sampling titration system per 0.5h, after theoretical value is reached, uses Constant pressure funnel control drop speed obtains final product branch polyurethane in 2 ~ 3s/ drops dropwise a certain amount of HEA of Deca, will be obtained Resin is cooled to 40 DEG C, adds the TEA neutralization reaction 1h of the identical molal quantitys of DMPA under high velocity agitation, and add water 1 h of emulsifying, quiet Acetone is removed with Rotary Evaporators after putting froth breaking organic-silicon-modified many arm type aqueous polyurethanes are obtained；
（2）The preparation of cured film
Weigh polyaminoester emulsion, add the water-soluble photoinitiator of gross mass 5%, add a certain amount of levelling agent, coalescents, Defoamer, after being stirred at room temperature uniformly, solution is poured in Teflon mold, and room temperature places 24 h, and 60 DEG C of baking ovens dry 2h, then will Film carries out solidification 40s and obtains cross-linked polyurethane film in being put into uviol lamp photo solidification machine.
2. the preparation method of cross-linked polyurethane film according to claim 1, it is characterised in that：Described IPDI is different fluorine That ketone diisocyanate, DBTDL is dibutyl tin laurate, and PCDL is PCDL, and THPDMS is terminal hydroxy group Polyether modified silicon oil.
CN201611014993.3A 2016-11-18 2016-11-18 Method for preparing cross-linked polyurethane film Pending CN106519163A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109705306A (en) * 2018-12-13 2019-05-03 江南大学 A kind of UV solidifies the preparation method of dimethyl silicone polymer base modified, weather resisting coating

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109705306A (en) * 2018-12-13 2019-05-03 江南大学 A kind of UV solidifies the preparation method of dimethyl silicone polymer base modified, weather resisting coating
CN109705306B (en) * 2018-12-13 2021-02-26 江南大学 Preparation method of UV-cured polydimethylsiloxane-based modified weather-resistant coating

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Application publication date: 20170322