CN113736418B - Modified single-component polyurethane foam joint mixture and preparation method thereof - Google Patents

Modified single-component polyurethane foam joint mixture and preparation method thereof Download PDF

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Publication number
CN113736418B
CN113736418B CN202111096819.9A CN202111096819A CN113736418B CN 113736418 B CN113736418 B CN 113736418B CN 202111096819 A CN202111096819 A CN 202111096819A CN 113736418 B CN113736418 B CN 113736418B
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polyurethane foam
component polyurethane
hours
raw materials
mixture
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CN113736418A (en
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张洪秀
吕征阳
吕政昊
郭焕
李蒙
吕品
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Liaoning Lvshi Chemical Group Co ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04Polyurethanes
    • C09J175/08Polyurethanes from polyethers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/16Catalysts
    • C08G18/161Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • C08G18/165Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22 covered by C08G18/18 and C08G18/24
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/16Catalysts
    • C08G18/18Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20Heterocyclic amines; Salts thereof
    • C08G18/2081Heterocyclic amines; Salts thereof containing at least two non-condensed heterocyclic rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/16Catalysts
    • C08G18/22Catalysts containing metal compounds
    • C08G18/24Catalysts containing metal compounds of tin
    • C08G18/244Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/61Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic

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  • 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 modified single-component polyurethane foam joint mixture and a preparation method thereof. The modified single-component polyurethane foam joint mixture is prepared from the following raw materials in percentage by weight: 5-18% of polyether polyol, 10-25% of organosilicon polymer, 0.4-0.8% of main catalyst, 0.05-0.15% of auxiliary catalyst, 0.5-2% of cross-linking agent, 0.005-0.02% of antioxidant, 0.05-0.25% of ultraviolet absorbent, 1-2% of silicone oil 8871, 30-40% of chlorinated paraffin, 10-18% of polymeric MDI, 8-15% of dimethyl ether and 4-15% of propane-butane. According to the invention, by adding the organosilicon polymer and the antioxidant and the ultraviolet absorber, yellowing of the foam beaten by the single-component polyurethane foam joint mixture can be effectively prevented and delayed, and the foam temperature resistance can be improved.

Description

Modified single-component polyurethane foam joint mixture and preparation method thereof
Technical Field
The invention relates to the technical field of building sealing and decoration, in particular to a modified single-component polyurethane foam joint mixture and a preparation method thereof.
Background
The one-component polyurethane foam caulking agent is a foam product of polyurethane applied in the aerosol technology. The adhesive has the advantages of simple operation, convenient use, excellent adhesion, heat insulation, heat preservation and the like, and is rapidly and widely applied to the fields of building sealing, decoration and fitment and the like.
In the current market, the single-component polyurethane foam joint mixture products all use polyether polyol and polymeric MDI as main raw materials, and because the benzene ring is directly connected with isocyanate groups, the large pi bond on the benzene ring and the adjacent NCO form conjugation. Under the action of light, heat and oxygen, especially ultraviolet rays, the urethane bond is initiated to be decomposed, so that the aromatic amine is generated. After oxidation rearrangement, the benzene nucleus on the aromatic amine generates a quinoid structure and other chromophoric groups, so that the polyurethane foam is easy to yellow and can not be kept exposed to the air for a long time. Meanwhile, the heat-resistant temperature of the polyurethane foam is in the range of-20 to 120 ℃, and the polyurethane foam is over-high in temperature and easy to deform and shrink; the temperature is too low, and the foam is brittle and has poor flexibility.
Disclosure of Invention
Aiming at the technical problems, the invention aims to provide a modified single-component polyurethane foam joint mixture and a preparation method thereof. According to the invention, by adding the organosilicon polymer and the antioxidant and the ultraviolet absorber, yellowing of the foam beaten by the single-component polyurethane foam joint mixture can be effectively prevented and delayed, and the foam temperature resistance can be improved.
The technical scheme adopted by the invention is as follows: a modified single-component polyurethane foam joint mixture is prepared from the following raw materials in percentage by weight:
further, the modified one-component polyurethane foam joint mixture is characterized in that the organosilicon polymer is one or two selected from alpha, omega-dihydroxy polydimethylsiloxane and hydroxyl-terminated polyether modified polysiloxane.
Further, the main catalyst is dimorpholine diethyl ether (DMDEE).
Further, the modified one-component polyurethane foam caulking agent is characterized in that the auxiliary catalyst is selected from dibutyl tin dilaurate or stannous octoate.
Further, the modified one-component polyurethane foam joint mixture is characterized in that the cross-linking agent is selected from methyltrimethoxysilane, methyltrionoxime silane, methyltriacetoxy silane or vinyltributylketoxime silane.
Further, the modified single-component polyurethane foam joint mixture is one or two selected from dibutyl cresol, tertiary butyl p-hydroxy anisole, antioxidant 245, antioxidant 30N, sodium thiosulfate and triphenyl phosphite.
Further, the modified one-component polyurethane foam joint compound is characterized in that the ultraviolet absorber is one or two selected from UV-1, UV-196, UV NP3 and Pub-380.
A preparation method of a modified single-component polyurethane foam joint mixture comprises the following steps:
1) Preparing materials according to the proportion;
2) Sequentially adding polyether polyol, organosilicon polymer, main catalyst, auxiliary catalyst, cross-linking agent, antioxidant, ultraviolet absorber, silicone oil 8871 and chlorinated paraffin into a mixer, mixing and stirring for 1-2 hours to obtain a mixture;
3) Putting the mixture obtained in the step 2) into an aerosol can, then adding polymeric MDI, sealing, filling dimethyl ether and propane by a filling machine, capping, shaking for 30-60 hours, and standing at room temperature for 48 hours to obtain the product.
The beneficial effects of the invention are as follows:
1. in the present invention, a silicone polymer is introduced as a raw material. The molecular chain of the organosilicon polymer mainly contains Si-O bond, and the bond energy is larger than the energy of ultraviolet rays, so that the single-component polyurethane foam joint mixture added with the organosilicon polymer can keep good performance under the irradiation of ultraviolet rays, and effectively prevent or delay aging and yellowing. And because the temperature resistant range of the organosilicon polymer is between-60 and 300 ℃, the single-component polyurethane foam joint mixture introduces the organosilicon polymer structure, and the high temperature resistance and the low temperature resistance of the foam are also improved. Meanwhile, a part of organosilicon polymer can form a network structure through an auxiliary catalyst and a cross-linking agent, so that the organosilicon polymer does not need to react with more polymeric MDI, the dosage of the polymeric MDI is reduced, and the conjugation quantity of large pi bonds on benzene rings and adjacent NCO is reduced. Namely, under the action of light, heat and oxygen, especially ultraviolet rays, the number of chromophoric groups such as quinoid structures and the like is reduced, thereby preventing and delaying the yellowing trend of the product.
2. In the invention, the auxiliary catalyst plays a role in improving the reaction speed of the organosilicon polymer, and mainly dibutyl tin dilaurate or stannous octoate is selected. Because the reaction speed of the organosilicon polymer is lower than that of the polyether polyol, the reaction speed between the organosilicon polymer and the polyether polyol can be effectively improved by increasing the auxiliary catalyst, a mixed chain segment can be better formed, and the generation of an intermediate prepolymer is promoted.
3. In the invention, the cross-linking agent has the main function of changing the organosilicon polymer from chain molecules to a net cross-linking state, accelerating the curing process, and more effectively improving the structure and stability of the cured foam, thereby improving the ageing resistance and yellowing resistance of the product.
4. In the invention, the antioxidant is added, so that the peroxide free radical can be captured or the hydroperoxide can be decomposed, and the yellowing of polyurethane can be effectively prevented or delayed.
5. In the invention, the ultraviolet absorber is added, so that ultraviolet can be effectively absorbed, and yellowing of polyurethane can be prevented.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
The modified single-component polyurethane foam joint mixture comprises the following components in proportion:
the preparation method (II) is as follows
1) Weighing various raw materials according to the proportion of the raw materials;
2) Sequentially adding the weighed polyether polyol, alpha, omega-dihydroxypolydimethylsiloxane, DMDEE, dibutyl tin dilaurate, methyltrionoxime silane, antioxidant 245, UV-196, silicone oil 8871 and chlorinated paraffin into a 1L mixer with a stirring device, and mixing and stirring for 2 hours to obtain a mixture;
3) Adding the mixture obtained in the step 2) into an aerosol can, then adding polymeric MDI, and sealing; and filling dimethyl ether and propane by a special filling machine, pressing, shaking for 60 hours at room temperature, and standing for 48 hours to obtain the modified single-component polyurethane foam joint mixture, wherein the product performance is shown in table 1.
Example 2
The modified single-component polyurethane foam joint mixture comprises the following components in proportion:
the preparation method (II) is as follows
1) Weighing various raw materials according to the proportion of the raw materials;
2) Sequentially adding weighed polyether polyol, alpha, omega-dihydroxypolydimethylsiloxane, hydroxyl-terminated polyether modified polysiloxane, DMDEE, stannous octoate, vinyl tributyl ketoxime silane, an antioxidant 30N, UV NP3, silicone oil 8871 and chlorinated paraffin into a 1L mixer with a stirring device, and mixing and stirring for 2 hours to obtain a mixture;
3) Adding the mixture obtained in the step 2) into an aerosol can, then adding polymeric MDI, and sealing; and filling dimethyl ether and propane by a special filling machine, pressing, shaking for 60 hours at room temperature, and standing for 48 hours to obtain the modified single-component polyurethane foam joint mixture, wherein the product performance is shown in table 1.
Example 3
The modified single-component polyurethane foam joint mixture comprises the following components in proportion:
the preparation method (II) is as follows
1) Weighing various raw materials according to the proportion of the raw materials;
2) Sequentially adding weighed polyether polyol, alpha, omega-dihydroxypolydimethylsiloxane, hydroxyl-terminated polyether modified polysiloxane, DMDEE, dibutyl tin dilaurate, methyltrionoxime silane, an antioxidant 30N, UV NP3, pub-380, silicone oil 8871 and chlorinated paraffin into a 1L mixer with a stirring device, and mixing and stirring for 2 hours to obtain a mixture;
3) Adding the mixture obtained in the step 2) into an aerosol can, then adding polymeric MDI, and sealing; and filling dimethyl ether and propane by a special filling machine, pressing, shaking for 60 hours at room temperature, and standing for 48 hours to obtain the modified single-component polyurethane foam joint mixture, wherein the product performance is shown in table 1.
TABLE 1 comparative Table of results for conventional one-component polyurethane foam caulking compositions and inventive embodiment data
Note that: the higher the ΔYI value, the more severe the yellowing.
As can be seen from Table 1, the modified single-component polyurethane foam caulking agent prepared by the invention improves the ultraviolet resistance and yellowing resistance of the product, and also improves the temperature resistance of the polyurethane foam. According to the invention, the Si-O bond in the polyurethane chain segment is increased by introducing the organosilicon polymer, the ultraviolet resistance is increased, the dosage of polymeric MDI is reduced, the generation of chromophoric groups is reduced, the chain segment network structure is improved by adding the cross-linking agent, and yellowing of the single-component polyurethane foam joint filling agent is prevented or delayed by adding the antioxidant and the ultraviolet absorber. Meanwhile, si-O bonds are introduced into the molecular chains and a net structure is enlarged, so that the high temperature resistance and the low temperature resistance of the single-component polyurethane foam joint mixture are improved.

Claims (3)

1. The modified single-component polyurethane foam gap filler is characterized by being prepared from the following raw materials in parts by weight:
polyether polyol 76.8. 76.8 g
Alpha, omega-dihydroxy polydimethylsiloxane 96 g
DMDEE 3.84 g
Dibutyl tin dilaurate 0.48 g
Methyl trione oxime silane 4.8g
Antioxidant 245.1 g
UV-196 0.48 g
Silicone oil 8871.6 g
287.9g of chlorinated paraffin
Polymeric MDI 113g
Dimethyl ether 75 g
Propane 82 g
The preparation method comprises the following steps:
1) Weighing various raw materials according to the proportion of the raw materials;
2) Sequentially adding the weighed polyether polyol, alpha, omega-dihydroxypolydimethylsiloxane, DMDEE, dibutyl tin dilaurate, methyltrionoxime silane, antioxidant 245, UV-196, silicone oil 8871 and chlorinated paraffin into a 1L mixer with a stirring device, and mixing and stirring for 2 hours to obtain a mixture;
3) Adding the mixture obtained in the step 2) into an aerosol can, then adding polymeric MDI, and sealing; and filling dimethyl ether and propane by a filling machine, capping, shaking for 60 hours, and standing at room temperature for 48 hours to obtain the modified single-component polyurethane foam joint mixture.
2. The modified single-component polyurethane foam gap filler is characterized by being prepared from the following raw materials in parts by weight:
polyether polyol 65.9 g
Alpha, omega-dihydroxy polydimethylsiloxane 84.8 g
Hydroxyl terminated polyether modified polysiloxane 33 g
DMDEE 2.8 g
Stannous octoate 0.7. 0.7 g
Vinyl tributylketoximino silane 7g
Antioxidant 30N 0.05g
UV NP3 0.45 g
Silicone oil 8871.1 g
Chlorinated paraffin 262.2 g
Polymeric MDI 122g
Dimethyl ether 72g
Propane butane 85g
The preparation method comprises the following steps:
1) Weighing various raw materials according to the proportion of the raw materials;
2) Sequentially adding weighed polyether polyol, alpha, omega-dihydroxypolydimethylsiloxane, hydroxyl-terminated polyether modified polysiloxane, DMDEE, stannous octoate, vinyl tributyl ketoxime silane, an antioxidant 30N, UV NP3, silicone oil 8871 and chlorinated paraffin into a 1L mixer with a stirring device, and mixing and stirring for 2 hours to obtain a mixture;
3) Adding the mixture obtained in the step 2) into an aerosol can, then adding polymeric MDI, and sealing; and filling dimethyl ether and propane by a filling machine, capping, shaking for 60 hours, and standing at room temperature for 48 hours to obtain the modified single-component polyurethane foam joint mixture.
3. The modified single-component polyurethane foam gap filler is characterized by being prepared from the following raw materials in parts by weight:
polyether polyol 59.4g
Alpha, omega-dihydroxy polydimethylsiloxane 89 g
Hydroxyl-terminated polyether modified polysiloxane 35 g
DMDEE 3 g
Dibutyl tin dilaurate 0.74. 0.74 g
Methyltrionooximino silane 9.9g
Antioxidant 30N 0.1g
UV NP3 0.6g
Pub-380 0.4g
Silicone oil 8871.4 g
Chlorinated paraffin 284.46g
Polymeric MDI 98g
Dimethyl ether 80g
Propane-butane 77g
The preparation method comprises the following steps:
1) Weighing various raw materials according to the proportion of the raw materials;
2) Sequentially adding weighed polyether polyol, alpha, omega-dihydroxypolydimethylsiloxane, hydroxyl-terminated polyether modified polysiloxane, DMDEE, dibutyl tin dilaurate, methyltrionoxime silane, an antioxidant 30N, UV NP3, pub-380, silicone oil 8871 and chlorinated paraffin into a 1L mixer with a stirring device, and mixing and stirring for 2 hours to obtain a mixture;
3) Adding the mixture obtained in the step 2) into an aerosol can, then adding polymeric MDI, and sealing; and filling dimethyl ether and propane by a filling machine, capping, shaking for 60 hours, and standing at room temperature for 48 hours to obtain the modified single-component polyurethane foam joint mixture.
CN202111096819.9A 2021-09-18 2021-09-18 Modified single-component polyurethane foam joint mixture and preparation method thereof Active CN113736418B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1616577A (en) * 2004-09-21 2005-05-18 济南大学 Organic silicon modified polyurethane gap-filling rubber for cement road
CN105969287A (en) * 2016-05-31 2016-09-28 苏州市奎克力电子科技有限公司 Transparent waterproof encapsulating material
CN106317854A (en) * 2016-08-24 2017-01-11 广东三和化工科技有限公司 Single-component polyurethane foam joint mixture and preparing method thereof
CN109628052A (en) * 2018-11-01 2019-04-16 保定赞伯商贸有限公司 A kind of polyurethane gap filler and preparation method thereof
CN110437420A (en) * 2019-08-02 2019-11-12 汾阳市绿健塑胶材料制造有限公司 A kind of modified polyurethane glue and preparation method thereof for plastic cement race track waterproof layer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1616577A (en) * 2004-09-21 2005-05-18 济南大学 Organic silicon modified polyurethane gap-filling rubber for cement road
CN105969287A (en) * 2016-05-31 2016-09-28 苏州市奎克力电子科技有限公司 Transparent waterproof encapsulating material
CN106317854A (en) * 2016-08-24 2017-01-11 广东三和化工科技有限公司 Single-component polyurethane foam joint mixture and preparing method thereof
CN109628052A (en) * 2018-11-01 2019-04-16 保定赞伯商贸有限公司 A kind of polyurethane gap filler and preparation method thereof
CN110437420A (en) * 2019-08-02 2019-11-12 汾阳市绿健塑胶材料制造有限公司 A kind of modified polyurethane glue and preparation method thereof for plastic cement race track waterproof layer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
曹云来.紫外线吸收剂.《密封胶—技术、配方、应用》.化学工业出版社,2001,(第1版), *

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