CN113501931A - Solvent-free low-viscosity isocyanate composition and preparation method and application thereof - Google Patents

Solvent-free low-viscosity isocyanate composition and preparation method and application thereof Download PDF

Info

Publication number
CN113501931A
CN113501931A CN202110526949.5A CN202110526949A CN113501931A CN 113501931 A CN113501931 A CN 113501931A CN 202110526949 A CN202110526949 A CN 202110526949A CN 113501931 A CN113501931 A CN 113501931A
Authority
CN
China
Prior art keywords
isocyanate composition
isocyanurate
diisocyanate
solvent
free low
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110526949.5A
Other languages
Chinese (zh)
Other versions
CN113501931B (en
Inventor
路富有
石滨
尚永华
孙立冬
李海军
王暖程
王勤隆
陈杰
张晓鹏
黎源
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wanhua Chemical Group Co Ltd
Original Assignee
Wanhua Chemical Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wanhua Chemical Group Co Ltd filed Critical Wanhua Chemical Group Co Ltd
Priority to CN202110526949.5A priority Critical patent/CN113501931B/en
Publication of CN113501931A publication Critical patent/CN113501931A/en
Application granted granted Critical
Publication of CN113501931B publication Critical patent/CN113501931B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
    • 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
    • C08G18/48—Polyethers
    • 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
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/725—Combination of polyisocyanates of C08G18/78 with other polyisocyanates
    • 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
    • C08G18/73—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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers

Landscapes

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

Abstract

The invention discloses a solvent-free low-viscosity isocyanate composition, a preparation method and application thereof, wherein the isocyanate composition is prepared from the following raw material components: a. an aliphatic diisocyanate; b. aliphatic polyisocyanurates; c. polyether polyols having a molecular weight of 1000-; d. at least one alkoxysilane isocyanurate compound. The isocyanate composition has the characteristics of no addition of solvent, low viscosity and excellent comprehensive mechanical property.

Description

Solvent-free low-viscosity isocyanate composition and preparation method and application thereof
Technical Field
The invention relates to an isocyanate composition, in particular to a solvent-free low-viscosity isocyanate composition, a preparation method and application thereof.
Background
Polyurethane resins are widely used in the fields of coatings, adhesives, sealants, elastomers, foams, printing inks, and the like. In the application fields, the polyurethane sealant is taken as an important branch of the polyurethane sealant, and has the remarkable characteristics of high mechanical strength, good low-temperature flexibility, excellent weather resistance and wear resistance and the like. Particularly in the automobile field, when the automobile frame material and the windshield have larger expansion coefficients, the polyurethane sealant can more outstand high elongation and good elastic recovery capability. The isocyanate component is the most main raw material for preparing the polyurethane resin, but the isocyanate monomer is limited to be widely applied due to the defects of long forming and curing time, insufficient crosslinking density and the like. Therefore, in practical applications, the isocyanate component is often used as a two-component polyurethane curing agent in the form of an isocyanate prepolymer, a self-assembly polymer or the like, and therefore, research on the isocyanate component is of great significance in the field of research and development of polyurethane products.
Chinese patent publication CN102643407A firstly adopts trimethylolpropane and polyhydric alcohol to modify isophorone diisocyanate, and then carries out trimerization reaction to prepare modified isocyanate prepolymer, and the final product has good compatibility with hydroxyl resin and good mechanical property; however, the method has complicated steps, the viscosity of the final product system is high, and an organic solvent is required to be added to reduce the viscosity when the method is used, so that the method is not favorable for the environment and the health of constructors; in addition, in the field of the sealant, the filling and coating thicknesses of the sealant are large, and the added organic solvent is difficult to escape completely, so that micro bubbles exist in the cured and molded product, and the curing quality of the product is seriously influenced. In addition, the performance of the glass sealant also relates to the structural property of the sealant, and the prepolymer system has the characteristics of high viscosity, single structure and insufficient bonding strength, and is difficult to meet the use requirement.
Chinese patent publication CN101880516A discloses that vegetable oil modified polyol and polyester polyol are firstly used to perform prepolymerization reaction on diphenylmethane diisocyanate, and then trimerization catalyst is added to perform polymerization reaction, so as to obtain isocyanate prepolymer, wherein the prepolymer is used without organic solvent, the content of free diphenylmethane diisocyanate is low, but the final NCO content of the prepolymer is also low, and the low NCO content can cause the adhesive to have the points of low curing speed, excessive viscosity and poor leveling property in the using process.
In view of the above, there is a strong need for an isocyanate composition for glass sealants that is solvent-free, has low viscosity and excellent overall mechanical properties.
Disclosure of Invention
The invention aims to provide an isocyanate composition which is free from solvent, low in viscosity and excellent in comprehensive mechanical properties, and a preparation method thereof.
Another object of the present invention is to provide a use of the above isocyanate composition for preparing a polyurethane-glass sealant material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a solvent-free low-viscosity isocyanate composition is prepared from the following raw material components:
a. an aliphatic diisocyanate;
b. aliphatic polyisocyanurates;
c. polyether polyols having a molecular weight of 1000-;
d. at least one alkoxysilane isocyanurate compound represented by the following general formula I,
Figure BDA0003065962440000031
in the general formula I, R1Is C1-C8 alkyl, R2、R3、R4Each independently is an alkyl or alkoxy group having a carbon number of C1-C4, and R2、R3、R4In which at least one is an alkoxy group, preferably R2、R3、R4Containing two or three alkoxy groups.
In the components, the aliphatic isocyanate has excellent weather resistance and yellowing resistance, and the polymerized polyisocyanurate has a monocyclic or polycyclic structure, stable cyclic structure and high mechanical strength. The polyether polyol is used as soft forging in a microphase separation structure, the structural parameters of the polyether polyol can influence the diffusion movement effect of sealant molecules between bonding layers, and carbon-carbon long chains in the structure can be used as intramolecular rotation nodes to adjust and improve the toughness and microphase crystallization degree of the material.
In the structure of the alkoxy silane isocyanurate compound, the six-membered ring structure of the isocyanurate is stable, and has the characteristics of chemical resistance and excellent mechanical property, the alkoxy silane isocyanurate compound is used as a coupling agent and an adhesive to be added into the composition system, and the special alkoxy silane isocyanurate structure and carbamate or trimer can form a vertically stacked hydrogen bond effect, so that the migration out of a resin main body is avoided, the system has a stronger adhesive effect compared with the conventional micromolecular monosiloxane structure, the effect of further improving the isocyanate composition is achieved, and the composition is suitable for multi-occasion application.
Further, the addition amounts of the raw material components are respectively as follows:
25-60%, preferably 30-55% of aliphatic diisocyanate;
30-65%, preferably 35-60%;
polyether polyols 5-25%, preferably 8-20%;
the alkoxysilane isocyanurate compound is 0.5 to 5%, preferably 2 to 4%.
According to the invention, the content of the components a, b, c and d is controlled, so that the isocyanate composition can be ensured to have lower viscosity, and the isocyanate composition can be more quickly permeated into tiny gaps of a bonding material when being applied to a sealant, and the sealing and bonding effects are improved.
Further, the aliphatic diisocyanate is selected from at least one of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and methylcyclohexyl diisocyanate, and is preferably selected from at least one of hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate.
Further, the aliphatic polyisocyanurate is at least one selected from the group consisting of hexamethylene diisocyanate trimer (HDI trimer), isophorone diisocyanate trimer (IPDI trimer), dicyclohexylmethane diisocyanate trimer (HMDI trimer).
Further, the polyether polyol is at least one selected from the group consisting of a polypropylene oxide polyether polyol, a polyethylene oxide polyether polyol, and a polypropylene oxide-ethylene oxide ether copolymer polyol, preferably at least one selected from the group consisting of a polypropylene oxide polyether polyol and a polypropylene oxide-ethylene oxide polyether polyol, and more preferably a polypropylene oxide polyether polyol.
The initiator of the polyether polyol can be dihydric alcohol, trihydric alcohol or tetrahydric alcohol. The diol may be, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1, 4-butanediol, 1, 3-butanediol, neopentyl glycol, trimethylpentanediol, cyclohexanedimethanol, 1, 5-pentanediol or 1, 6-hexanediol. The triol may be, for example, trimethylolpropane, ethoxylated trimethylolpropane, glycerol or castor oil. The tetrahydric alcohol may be, for example, pentaerythritol.
Further, the alkoxysilane isocyanurate compound is 1,3, 5-tris (trimethoxysilylpropyl) isocyanurate, 1,3, 5-tris (methyldimethoxysilylpropyl) isocyanurate, 1,3, 5-tris (methyldiethoxysilylpropyl) isocyanurate, 1,3, 5-tris (trimethoxysilylbutyl) isocyanurate, one or more of 1,3,5- (methyldimethoxysilylbutyl) isocyanurate and 1,3, 5-tris (triethoxysilylpropyl) isocyanurate, preferably one or two of 1,3, 5-tris (trimethoxysilylpropyl) isocyanurate and 1,3, 5-tris (trimethoxysilylbutyl) isocyanurate.
Further, the alkoxysilane isocyanurate compound can be prepared by a condensation method, a trimerization method, a cracking method, an addition method and the like, and specific preparation methods can be prepared by referring to Chinese patents CN109824715A, CN101805366A, CN101189246B and CN101189247B or U.S. Pat. No. 3, 2006235221A1, or commercial products of the type can be directly purchased.
Further, the raw material components for preparing the isocyanate composition further include a catalyst which can promote the formation of a urethane structure, and the amount of the catalyst added is 0.001 to 1%, preferably 0.01 to 0.05% of the total mass of the raw material components a, b, c, and d.
Further, the catalyst is a metal salt catalyst or a tertiary amine catalyst, the metal salt catalyst is preferably at least one of dibutyltin dilaurate, stannous octoate, iron acetylacetonate, zinc octoate, lead octoate and potassium oleate, and the tertiary amine catalyst is preferably at least one of triethylamine, pyridine, picoline, benzyldimethylamine, N-dimethylcyclohexylamine, N-methylpiperidine, pentamethyldiethylenetriamine, N-ethylenepiperazine and N, N-dimethylpiperazine; the catalyst is preferably at least one selected from dibutyltin dilaurate, stannous octoate and N, N-dimethyl cyclohexylamine.
Preferably, in the above isocyanate composition of the present invention, the viscosity of the isocyanate composition at 25 ℃ is 500-;
preferably, in the above isocyanate composition of the present invention, the content of free isocyanate groups in the isocyanate composition is 15 to 35%, preferably 17 to 28%, more preferably 20 to 26%.
The viscosity of the isocyanate composition and/or the content of free isocyanate groups (-NCO) are within the above range, so that the composition has relatively low operating viscosity, the use of an organic solvent is avoided during customer construction, no closed-cell phenomenon exists in the finally formed sealant material, and the mechanical property of the material is improved.
A preparation method of the solvent-free low-viscosity isocyanate composition comprises the following steps:
adding the selected aliphatic diisocyanate into a reaction container under the atmosphere of inert gas, adding the selected aliphatic polyisocyanurate into the container, stirring and heating to 35-120 ℃, adding a catalyst, and slowly dropwise adding the selected polyether polyol into the reaction container for 0.5-4 hours; after the dripping of the polyol is finished, continuously reacting for 1-4h at 35-120 ℃, then adding the alkoxy silane isocyanurate compound, and stirring and mixing uniformly to obtain the isocyanate composition.
In the above production method, the inert atmosphere is preferably nitrogen.
An automotive glass sealant is prepared by taking the isocyanate composition as a curing agent.
Methods for preparing automotive glass sealants from isocyanate compositions are well known in the art. The following process is preferably used in the present invention to prepare polyurethane sealants from isocyanate compositions: under the conditions that the relative humidity is lower than 35 percent at the temperature of 15-35 ℃, 40-80 parts of polyether polyol A with the three functionality and the molecular weight of 2000-6000 daltons, 10-40 parts of polyether polyol B with the two functionality and the molecular weight of 800-2500 daltons and 10-20 parts of carbon black filler are respectively added into a glue making container, 0.01-1 percent of any auxiliary agent and 200-1500ppm of catalyst based on the total mass of the polyether polyol A, B and the carbon black filler are added, after the mixture is mechanically stirred and mixed uniformly, an isocyanate composition is added according to the NCO/OH ratio of 1.0-1.1, the mixture is mechanically stirred for 3-8 minutes and is uniformly mixed, the mixture is vacuumized at the room temperature to remove bubbles, then the mixture is poured into a standard die and is cured for 0.5-4 hours at the temperature of 80-120 ℃, after the mixture is cured for 8-48 hours at the room temperature, finally obtaining the polyurethane-glass sealant resin sample strip.
The auxiliary agent can be one or a mixture of any more of auxiliary agents such as a defoaming agent, a wetting agent, a dispersing agent, a flatting agent, a silane coupling agent and the like.
According to the invention, the research shows that the isocyanate composition prepared by mixing the aliphatic diisocyanate and the polyisocyanurate according to a certain proportion, carrying out co-reaction and pre-polymerization on the mixture by using the polyether polyol with specific parameter ranges, and then introducing the alkoxysilane isocyanurate for blending modification has the advantages of no solvent, low viscosity and good comprehensive mechanical property, and can obviously improve the construction efficiency and the comprehensive mechanical property of the polyurethane-sealant, so that the isocyanate composition is particularly suitable for the field of polyurethane-glass sealants.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
The following examples and comparative examples of the present invention have the following main raw materials and sources:
isophorone diisocyanate (IPDI), Van Waals chemical group, Inc.;
hexamethylene Diisocyanate (HDI), Vanhua chemical group, Inc.;
pentamethylene Diisocyanate (PDI), wanhua chemical group ltd;
IPDI trimer, aliphatic polyisocyanurate, wanhua chemical group, inc;
HDI trimer, aliphatic polyisocyanurate, Vanhua chemical group, Inc.;
wanol F3128, polypropylene oxide-ethylene oxide polyether polyol having an average functionality of 3, a molecular weight of about 6000g/mol, a moisture content of <500ppm, from Wanol chemical group, inc;
puranol D240, a polypropylene oxide ether polyol having an average functionality of 3, a molecular weight of about 4000g/mol, a moisture content of <500ppm, from Excellent Chemicals Inc.;
wanol C2020, a polypropylene oxide ether polyol having an average functionality of 2, a molecular weight of about 2000g/mol, a moisture content of <500ppm, from Wanol chemical group, inc;
wanol C2004, polypropylene oxide ether polyol, having an average functionality of 2, a molecular weight of about 410g/mol, a moisture content of <500ppm, from Wanol chemical group, inc;
wanol R2307, a polypropylene oxide ether polyol having an average functionality of 4, a molecular weight of about 680g/mol, a moisture content of <500ppm, from Wanol chemical group, inc;
wanol F3135, a commonly used polyether polyol for glass sealants, having an average functionality of 3 and a molecular weight of about 5000g/mol, was used as a copolymerization reactant for isocyanate compositions from Wanol chemical group, inc;
puranol D220, a commonly used polyether polyol for glass sealants having an average functionality of 2 and a molecular weight of about 2000g/mol, was used as a copolymerization reactant for isocyanate compositions, available from optimization chemical Co., Ltd;
t-33, 1,3, 5-tris (trimethoxysilylpropyl) isocyanurate available from Huaian Hongmeng New materials, Inc.;
KBM-9658, 1,3, 5-tris (trimethoxysilylbutyl) isocyanurate, commercially available from Fuller's silicone;
t-03, 3-isocyanatopropyl trimethoxysilane, available from Huaian Macrograph New materials Co., Ltd;
AD328, a composite auxiliary agent for polyurethane sealant, which is purchased from Guangzhou Honghai New Material science and technology Co., Ltd;
unless otherwise specified, the contents in the present invention are all mass contents.
In the following examples and comparative examples of the invention, the NCO content was measured according to the standard GB/T12009.4; dynamic viscosity was measured using a laminar viscometer (Brookfield DT-2) at 25 ℃.
[ example 1 ]
The preparation method of the isocyanate composition of this example comprises the following steps: under the nitrogen atmosphere, 0.400kg of IPDI and 0.500kg of HDI trimer are added into a reaction kettle, the mixture is heated to 80 ℃ under stirring, 0.36g of dibutyltin dilaurate is added, then 0.100kg of polyether polyol Wanol C2020 is slowly dripped into the reaction kettle to react, after dripping for 2h, the mixture is continuously stirred and reacted for 2h at 80 ℃, 0.030kg of alkoxy silane isocyanurate T-33 is added, and stirring and mixing are carried out for 30min, so that the isocyanate composition 1# is obtained. The NCO content was found to be 24.90% by analysis, and the viscosity to be 862cp/25 ℃.
[ example 2 ]
The preparation method of the isocyanate composition of this example comprises the following steps: under the nitrogen atmosphere, 0.400kg of IPDI and 0.490kg of IPDI trimer are firstly added into a reaction kettle, the mixture is heated to 80 ℃ under stirring, 0.270g of dibutyltin dilaurate is then added, 0.105kg of polyether polyol Wanol C2020 is slowly dripped into the reaction kettle to react, after dripping for 1h, the mixture is continuously stirred and reacted for 2h at 80 ℃, 0.006kg of alkoxy silane isocyanurate T-33 is then added, and stirring and mixing are carried out for 30min, thus obtaining the isocyanate composition No. 2. The NCO content was found to be 23.23% by analysis, and the viscosity was 1815cp/25 ℃.
[ example 3 ]
The preparation method of the isocyanate composition of this example comprises the following steps: under the nitrogen atmosphere, firstly adding 0.360kg PDI and 0.500kg IPDI tripolymer into a reaction kettle, heating to 80 ℃ under stirring, then adding 0.400g stannous octoate, then slowly dropwise adding 0.110kg polyether polyol Puranol D240 into the reaction kettle for reaction, after the dropwise adding is finished for 3h, continuously stirring and reacting for 2h at 80 ℃, then adding 0.030kg alkoxy silane isocyanurate T-33, and stirring and mixing for 30min to obtain the isocyanate composition No. 3. The NCO content was found to be 22.13% by analysis, and the viscosity was 2100cp/25 ℃.
[ example 4 ]
The preparation method of the isocyanate composition of this example comprises the following steps: under the nitrogen atmosphere, firstly adding 0.460kg of IPDI and 0.500kg of IPDI tripolymer into a reaction kettle, heating to 80 ℃ under stirring, then adding 0.230g of stannous octoate, then slowly dropwise adding 0.090kg of polyether polyol Wanol F3128 into the reaction kettle for reaction, after dropwise adding is finished for 4h, continuously stirring and reacting for 2h at 80 ℃, then adding 0.053kg of alkoxy silane isocyanurate T-33, and stirring and mixing for 30min to obtain the isocyanate composition No. 4. The NCO content was found to be 23.53% by analysis, and the viscosity to be 1678cp/25 ℃.
[ example 5 ]
The preparation method of the isocyanate composition of this example comprises the following steps: under the nitrogen atmosphere, 0.580kg of IPDI and 0.318kg of IPDI tripolymer are added into a reaction kettle, the mixture is heated to 80 ℃ under stirring, 0.360g N, N-dimethylcyclohexylamine is added, then 0.130kg of polyether polyol Wanol F3128 is slowly dripped into the reaction kettle for reaction, after dripping for 2 hours, the mixture is continuously stirred and reacted for 2 hours under 80 ℃, 0.025kg of alkoxy silane isocyanurate T-33 is added, and stirring and mixing are carried out for 30 minutes, thus obtaining the isocyanate composition No. 5. The NCO content was found to be 25.85% by analysis, and the viscosity to be 1069cp/25 ℃.
[ example 6 ]
The preparation method of the isocyanate composition of this example comprises the following steps: under the nitrogen atmosphere, 0.325kg of HDI and 0.625kg of IPDI trimer are added into a reaction kettle, the mixture is heated to 80 ℃ under stirring, 0.480g of dibutyltin dilaurate is added, then 0.300kg of polyether polyol Wanol F3128 is slowly dripped into the reaction kettle for reaction, after dripping for 2 hours, the mixture is continuously stirred and reacted for 2 hours at 80 ℃, 0.030kg of alkoxy silane isocyanurate T-33 is added, and stirring and mixing are carried out for 30 minutes, so as to obtain the isocyanate composition No. 6. The NCO content was 20.75% by analysis, and the viscosity was 2895cp/25 ℃.
[ example 7 ]
The preparation method of the isocyanate composition of this example comprises the following steps: under the nitrogen atmosphere, 0.370kg of HDI and 0.680kg of IPDI trimer are firstly added into a reaction kettle, the mixture is heated to 80 ℃ under stirring, 0.290g of dibutyltin dilaurate is then added, 0.070kg of polyether polyol Wanol F3128 is slowly dripped into the reaction kettle for reaction, after dripping for 2 hours, the mixture is continuously stirred and reacted for 2 hours under 80 ℃, 0.045kg of alkoxy silane isocyanurate KBM-9658 is then added, and stirring and mixing are carried out for 30 minutes, thus obtaining the isocyanate composition No. 7. The NCO content was found to be 25.97% by analysis, and the viscosity was 3700cp/25 ℃.
Comparative example 1
This comparative example differs from example 1 only in that: the polyether polyol Wanol C2020 in example 1 was replaced with polyether polyol Wanol C2004 and the remaining raw materials, experimental conditions and reaction steps were the same as in example 1 to give isocyanate composition 1' #. The NCO content was found to be 23.27% by analysis, and the viscosity was 1027cp/25 ℃.
Comparative example 2
This comparative example differs from example 2 only in that: the polyether polyol Wanol C2020 in example 2 was replaced by polyether polyol Wanol R2307 and the remaining raw materials, experimental conditions and reaction steps were the same as in example 2 to give isocyanate composition 2' #. The NCO content was found to be 21.78% by analysis, and the viscosity was 2103cp/25 ℃.
Comparative example 3
This comparative example differs from example 3 only in that: the amount of 0.360kg PDI used in example 3 was replaced with 0.00kg, and the remaining raw materials, experimental conditions and reaction procedures were the same as those of example 3, to give an isocyanate composition 3' #. The NCO content was found to be 13.31% by analysis, and the viscosity was 16890cp/25 ℃.
Comparative example 4
This comparative example differs from example 4 only in that: the amount of IPDI trimer used in example 4 was replaced with 0.00kg and the remaining raw materials, experimental conditions and reaction procedures were the same as in example 4 to give isocyanate composition 4' #. The NCO content was 28.52% and the viscosity was 425cp/25 ℃ by analysis.
Comparative example 5
This comparative example differs from example 5 only in that: the amount of alkoxysilane isocyanurate T-33 used in example 5 was replaced with 0.00kg and the remaining raw materials, experimental conditions and reaction steps were the same as in example 5 to give an isocyanate composition 5' #. The NCO content was 26.47% and the viscosity was 989cp/25 ℃ by analysis.
Comparative example 6
This comparative example differs from example 6 only in that: the remaining raw materials, experimental conditions and reaction procedures were the same as in example 6 except that 0.03kg of alkoxysilane isocyanurate T-33 of example 6 was replaced with 0.03kg of monoisocyanato-based alkoxysilane T-03, to give isocyanate composition 6' #. The NCO content was 20.80% by analysis, and the viscosity was 2758cp/25 ℃.
Comparative example 7
This comparative example differs from example 7 only in that: the amount of polyether polyol Wanol F3128 used in example 7 was replaced with 0.00kg and the remaining raw materials, experimental conditions and reaction procedures were the same as in example 7 to give an isocyanate composition 7' #. The NCO content was found to be 27.76% by analysis, and the viscosity was 3400cp/25 ℃.
[ example 8 ]
The preparation of the polyurethane-automotive glass sealant of the embodiment comprises the following steps: under the conditions that the relative humidity is lower than 35 percent at 15-35 ℃, 60g of polyether polyol Wanol F3135, 20g of polyether polyol Puranol D220 and 20g of carbon black filler are respectively added into a glue making container, 0.2g of composite additive AD328 and 0.1g of dibutyltin dilaurate are added into the glue making container, the mixture is mechanically stirred and uniformly mixed, the isocyanate composition prepared in the example 1 is metered according to the NCO/OH ratio of 1.05, the mixture is mechanically stirred for 3-8 minutes to be uniformly mixed, air bubbles are removed by vacuumizing at room temperature, the mixture is poured into a standard mold, the mixture is cured for 2 hours at 85 ℃, and the mixture is cured for 24 hours at room temperature to finally obtain the polyurethane-glass sealant resin.
[ examples 9 to 14 and comparative examples 8 to 14 ]
The preparation of the polyurethane-glass sealant resins of examples 9-14 and comparative examples 8-14 differed from example 8 only in that: the isocyanate composition of example 8 was replaced with the isocyanate compositions prepared in examples 2 to 7 and comparative examples 1 to 7, respectively, in this order, and the remaining reaction raw materials, reaction conditions and experimental procedures were the same as those of example 8.
Performance test of the polyurethane-glass sealant resin material:
the mechanical properties of the polyurethane-glass sealants prepared in examples 8 to 14 and comparative examples 8 to 14 were measured according to the following methods: the tensile strength and the elongation at break are tested according to a method for testing the tensile stress-strain performance of the vulcanized rubber and the thermoplastic rubber of GB/T528-2009, and a testing instrument adopts an FR-108C computer servo universal tensile testing machine of Shanghai Murui instrument science and technology Limited; the tearing strength is measured according to the method for measuring the tearing strength of the vulcanized rubber of GB/T528-1999, and a measuring instrument adopts a RWN-10KN rubber tearing strength measuring instrument of Beijing essence instrument company Limited; shore hardness A test instrument was a TIME-5430 Shore hardness meter, available from Peak technologies, Inc. of Beijing TIMEs, according to the method of ASTM D2240. The specific experimental results are shown in tables 1 and 2.
TABLE 1 Performance test results of the resin materials of examples 8 to 14
Figure BDA0003065962440000131
Note that in the above tables, "+" indicates good adhesion, "-" indicates poor adhesion, and "+" or "-" indicates degree.
TABLE 2 Performance test results of the resin materials of comparative examples 8 to 14
Figure BDA0003065962440000132
Note that in the above tables, "+" indicates good adhesion, "-" indicates poor adhesion, and "+" or "-" indicates degree.
As can be seen from tables 1 and 2, the polyurethane-glass sealant resin materials prepared in examples 8 to 14 are excellent in the indexes such as tensile strength, elongation at break and adhesion to a base material, and have better comprehensive properties; the polyurethane-glass sealant resin prepared in the comparative examples 8-14 obviously has the defects of poor indexes, poor comprehensive performance and difficulty in meeting the actual requirements.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.

Claims (10)

1. The solvent-free low-viscosity isocyanate composition is characterized by being prepared from the following raw material components:
a. an aliphatic diisocyanate;
b. aliphatic polyisocyanurates;
c. polyether polyols having a molecular weight of 1000-;
d. at least one alkoxysilane isocyanurate compound represented by the following general formula I,
Figure FDA0003065962430000011
in the general formula I, R1Is C1-C8 alkyl, R2、R3、R4Each independently is an alkyl or alkoxy group having a carbon number of C1-C4, and R2、R3、R4In which at least one is an alkoxy group, preferably R2、R3、R4Containing two or three alkoxy groups.
2. The solvent-free low-viscosity isocyanate composition according to claim 1, wherein the raw material components are added in the following amounts:
25-60%, preferably 30-55% of aliphatic diisocyanate;
30-65%, preferably 35-60%;
polyether polyols 5-25%, preferably 8-20%;
the alkoxysilane isocyanurate compound is 0.5 to 5%, preferably 2 to 4%.
3. Solvent-free low-viscosity isocyanate composition according to claim 1 or 2, wherein the aliphatic diisocyanate is at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and methylcyclohexyl diisocyanate, preferably at least one selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate.
4. A solvent-free low viscosity isocyanate composition according to claim 1 or 2 wherein the aliphatic polyisocyanurate is at least one selected from the group consisting of hexamethylene diisocyanate trimer, isophorone diisocyanate trimer and dicyclohexylmethane diisocyanate trimer.
5. Solvent-free low viscosity isocyanate composition according to claim 1 or 2, wherein the polyether polyol is selected from at least one of polypropylene oxide ether polyol, polyethylene oxide ether polyol, polypropylene oxide-ethylene oxide ether copolyol, preferably from at least one of polypropylene oxide ether polyol, polypropylene oxide-ethylene oxide ether polyol, more preferably from polypropylene oxide ether polyol.
6. Solvent-free low viscosity isocyanate composition according to claim 1 or 2, wherein the alkoxysilane isocyanurate compound is one or more of 1,3, 5-tris (trimethoxysilylpropyl) isocyanurate, 1,3, 5-tris (methyldimethoxysilylpropyl) isocyanurate, 1,3, 5-tris (methyldiethoxysilylpropyl) isocyanurate, 1,3, 5-tris (trimethoxysilylbutyl) isocyanurate, 1,3,5- (methyldimethoxysilylbutyl) isocyanurate, 1,3, 5-tris (triethoxysilylpropyl) isocyanurate, preferably 1,3, 5-tris (trimethoxysilylpropyl) isocyanurate, 1,3, one or two of 5-tris (trimethoxysilylbutyl) isocyanurate.
7. Solvent-free low-viscosity isocyanate composition according to claim 1 or 2, wherein the starting components for preparing the isocyanate composition further comprise a catalyst, and the catalyst is added in an amount of 0.001 to 1%, preferably 0.01 to 0.05% of the total mass of the starting components a, b, c and d.
8. The solvent-free low viscosity isocyanate composition according to claim 7, wherein the catalyst is a metal salt catalyst or a tertiary amine catalyst, the metal salt catalyst is at least one selected from dibutyltin dilaurate, stannous octoate, iron acetylacetonate, zinc octoate, lead octoate and potassium oleate, the tertiary amine catalyst is at least one selected from triethylamine, pyridine, picoline, benzyldimethylamine, N-dimethylcyclohexylamine, N-methylpiperidine, pentamethyldiethylenetriamine, N-ethylenepiperazine and N, N-dimethylpiperazine; the catalyst is preferably at least one selected from dibutyltin dilaurate, stannous octoate and N, N-dimethyl cyclohexylamine.
9. A process for the preparation of the solvent-free low viscosity isocyanate composition according to any one of claims 1 to 8 comprising the steps of:
adding the selected aliphatic diisocyanate into a reaction container under the atmosphere of inert gas, adding the selected aliphatic polyisocyanurate into the container, stirring and heating to 35-120 ℃, adding a catalyst, and slowly dropwise adding the selected polyether polyol into the reaction container for 0.5-4 hours; after the dripping of the polyol is finished, continuously reacting for 1-4h at 35-120 ℃, then adding the alkoxy silane isocyanurate compound, and stirring and mixing uniformly to obtain the isocyanate composition.
10. An automotive glass sealant characterized by being prepared by using the isocyanate composition according to any one of claims 1 to 8 as a curing agent.
CN202110526949.5A 2021-05-14 2021-05-14 Solvent-free low-viscosity isocyanate composition and preparation method and application thereof Active CN113501931B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110526949.5A CN113501931B (en) 2021-05-14 2021-05-14 Solvent-free low-viscosity isocyanate composition and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110526949.5A CN113501931B (en) 2021-05-14 2021-05-14 Solvent-free low-viscosity isocyanate composition and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113501931A true CN113501931A (en) 2021-10-15
CN113501931B CN113501931B (en) 2022-07-12

Family

ID=78008364

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110526949.5A Active CN113501931B (en) 2021-05-14 2021-05-14 Solvent-free low-viscosity isocyanate composition and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113501931B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113773501A (en) * 2021-09-08 2021-12-10 广东致格纳米科技有限公司 Preparation method of curable silicon-based hybrid resin
CN114015406A (en) * 2021-12-07 2022-02-08 江苏铁锚玻璃股份有限公司 Formula of polyurethane glue, preparation method of polyurethane glue and multilayer glass
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080057316A1 (en) * 2006-09-01 2008-03-06 General Electric Company Solid polymeric substrate having adherent resin component derived from curable silylated polyurethane composition
CN107446111A (en) * 2017-09-12 2017-12-08 万华化学集团股份有限公司 A kind of Silante terminated resin of amido-containing acid ester base and preparation method thereof
CN111154062A (en) * 2020-01-06 2020-05-15 万华化学集团股份有限公司 Isocyanate prepolymer for polyurethane-fiber composite material and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080057316A1 (en) * 2006-09-01 2008-03-06 General Electric Company Solid polymeric substrate having adherent resin component derived from curable silylated polyurethane composition
CN107446111A (en) * 2017-09-12 2017-12-08 万华化学集团股份有限公司 A kind of Silante terminated resin of amido-containing acid ester base and preparation method thereof
CN111154062A (en) * 2020-01-06 2020-05-15 万华化学集团股份有限公司 Isocyanate prepolymer for polyurethane-fiber composite material and preparation method and application thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113773501A (en) * 2021-09-08 2021-12-10 广东致格纳米科技有限公司 Preparation method of curable silicon-based hybrid resin
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
CN114015406A (en) * 2021-12-07 2022-02-08 江苏铁锚玻璃股份有限公司 Formula of polyurethane glue, preparation method of polyurethane glue and multilayer glass

Also Published As

Publication number Publication date
CN113501931B (en) 2022-07-12

Similar Documents

Publication Publication Date Title
CN113501931B (en) Solvent-free low-viscosity isocyanate composition and preparation method and application thereof
CN111154062B (en) Isocyanate prepolymer for polyurethane-fiber composite material and preparation method and application thereof
US4798878A (en) Synthetic resin compositions shelf-stable under exclusion of moisture
EP1465936B1 (en) Cross-linkable polymer blends containing alkoxysilane-terminated polymers
CN111748310B (en) Double-component polyurethane adhesive and preparation method thereof
CN114450323A (en) Low free polyurethane prepolymer compositions
DE102004035764A1 (en) Low viscosity polyurethane prepolymers based on 2,4&#39;-MDI
CN111909337B (en) Crosslinking agent, polyurethane prepolymer and single-component polyurethane adhesive
CN111808569B (en) Damp and heat resistant high-strength single-component polyurethane primer-free adhesive sealant and preparation method thereof
CN105037676B (en) A kind of PPDI based polyurethanes elastomers of low compression set and preparation method thereof
CN112210336A (en) Low-temperature-resistant polyurethane adhesive and preparation method thereof
US4902736A (en) One-part curing composition
CN112080244A (en) High-strength and fast-curing one-component primer-free polyurethane sealant and preparation method thereof
EP3747948B1 (en) Polyurethane resin composition
CN113429926B (en) Polyurethane adhesive and preparation method and application thereof
CN111171268B (en) Heat-resistant polyurethane soft foam and preparation method thereof
KR102271145B1 (en) Isocyanate prepolymer, moisture-curing polyurethane and eco-friendly adhesive composition comprising the same
CN115785850B (en) Adhesion promoter, preparation method and application thereof, and waterproof adhesive single-component polyurethane sealant, and preparation method and application thereof
CN116023626A (en) Hydrolysis-resistant high-solid-content closed polyurethane resin composition and preparation method thereof
KR20180016516A (en) Adhesive composition and method for producing the same
KR102351307B1 (en) Isocyanate prepolymer, moisture-curing polyurethane and eco-friendly adhesive composition comprising the same
CN107636037A (en) The manufacture method of urethane composition and urethane composition
CN110845695B (en) Water-swellable silane polyether type resin and preparation method thereof
CN117025155B (en) Double-component polyurethane adhesive for outdoor yacht, and preparation method and application thereof
EP2270060A1 (en) Moisture-curing polyurethane adhesive

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant