CN113667086A - Siloxane modified polyurea material and preparation method and application thereof - Google Patents
Siloxane modified polyurea material and preparation method and application thereof Download PDFInfo
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- 229920002396 Polyurea Polymers 0.000 title claims abstract description 88
- 239000000463 material Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims description 46
- 229920005989 resin Polymers 0.000 claims abstract description 57
- 239000011347 resin Substances 0.000 claims abstract description 57
- 238000003756 stirring Methods 0.000 claims abstract description 43
- 108010064470 polyaspartate Proteins 0.000 claims abstract description 37
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 53
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 53
- 150000002148 esters Chemical class 0.000 claims description 44
- 229920000805 Polyaspartic acid Polymers 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 25
- 125000003277 amino group Chemical group 0.000 claims description 19
- 229920000608 Polyaspartic Polymers 0.000 claims description 13
- 239000007822 coupling agent Substances 0.000 claims description 9
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 8
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000002787 reinforcement Effects 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- ZQTYRTSKQFQYPQ-UHFFFAOYSA-N trisiloxane Chemical compound [SiH3]O[SiH2]O[SiH3] ZQTYRTSKQFQYPQ-UHFFFAOYSA-N 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical group O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 claims description 3
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 2
- 238000000465 moulding Methods 0.000 abstract description 13
- 239000011083 cement mortar Substances 0.000 abstract description 10
- 239000002861 polymer material Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 17
- -1 amino compound Chemical class 0.000 description 15
- 238000002329 infrared spectrum Methods 0.000 description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 description 14
- 239000012948 isocyanate Substances 0.000 description 12
- 150000002513 isocyanates Chemical class 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- AUGNALLOZRFJAT-UHFFFAOYSA-N (1,2-diisocyanato-2-phenylethyl)benzene Chemical compound C=1C=CC=CC=1C(N=C=O)C(N=C=O)C1=CC=CC=C1 AUGNALLOZRFJAT-UHFFFAOYSA-N 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
- C08G18/28—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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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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)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开了一种硅氧烷改性聚脲材料及其制备方法和用途，属于高分子材料术领域。硅氧烷改性聚脲材料按照以下步骤进行制备：在惰性气体或真空下，先将聚天门冬氨酸酯树脂与二异氰酸酯搅拌反应，使其预聚，再加入硅烷偶联剂，搅拌反应0.5～4h后获得硅氧烷改性聚天门冬氨酸酯树脂；向硅氧烷改性聚天门冬氨酸酯树脂中加入含二个及以上异氰酸酯基团的固化剂，搅拌0.2～2min，混合均匀，固化成型得到硅氧烷改性聚脲材料。本发明制备的硅氧烷改性聚脲材料，提高了聚脲材料与水泥砂浆的附着力。
The invention discloses a siloxane-modified polyurea material, a preparation method and application thereof, and belongs to the field of polymer material technology. The siloxane-modified polyurea material is prepared according to the following steps: under inert gas or vacuum, firstly, the polyaspartate resin and diisocyanate are stirred and reacted to make it prepolymerized, and then the silane coupling agent is added, and the stirring reaction is carried out. After 0.5 to 4 hours, a siloxane-modified polyaspartate resin is obtained; a curing agent containing two or more isocyanate groups is added to the siloxane-modified polyaspartate resin, and the mixture is stirred for 0.2 to 2 minutes. Mixing uniformly, curing and molding to obtain the siloxane-modified polyurea material. The siloxane-modified polyurea material prepared by the invention improves the adhesion between the polyurea material and the cement mortar.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a siloxane modified polyurea material and a preparation method and application thereof.
Background
Polyurea materials are a class of organic high polymer materials with high performance, and the mechanical properties of the polyurea materials can be changed from elastomers to rigid bodies, so the polyurea materials have wide application. Conventional polyureas are elastomeric materials formed by the reaction of an isocyanate component (A component) and an amino compound component (B component) are representative of high-solids green resins. The special microstructure of the polyurea molecules endows the polyurea material with a plurality of excellent performances, compared with other polymer materials, the polyurea material has the characteristics of aging resistance, corrosion resistance, abrasion resistance, high temperature resistance, radiation resistance and the like, and also has higher strength, good elongation at break and thermal stability, and can be used for a long time in severe environment.
However, the polyurea material has larger thermal shrinkage rate and large internal stress in the preparation process, so that the adhesive force between the polyurea material and silicate matrix materials such as cement, mortar and the like is influenced. Based on the silicone modified polyurea material, the invention provides a silicone modified polyurea material, which can improve the adhesive force of polyurea and cement mortar, effectively solve the problems and expand the application of the polyurea and the cement mortar.
Disclosure of Invention
The invention provides a siloxane modified polyurea material, a preparation method and application thereof, which can improve the adhesive force of polyurea and cement mortar.
The first object of the present invention is to provide a method for preparing a silicone-modified polyurea material, which comprises the following steps:
under inert gas or vacuum, firstly stirring and reacting the polyaspartic ester resin with diisocyanate to pre-polymerize the resin, then adding a silane coupling agent, and stirring and reacting for 0.5-4 h to obtain siloxane modified polyaspartic ester resin;
adding a curing agent containing two or more isocyanate groups into the siloxane modified polyaspartic ester resin, stirring for 0.2-2 min, uniformly mixing, and curing and forming to obtain a siloxane modified polyurea material;
wherein in the prepolymerization reaction, the molar ratio of the isocyanic acid radical in the diisocyanate to the amino group in the polyaspartic acid ester resin is 0.1-0.3: 1, and the molar ratio of the silane coupling agent to the diisocyanate is 1: 1-23;
the molar ratio of the isocyanic acid radical in the curing agent to the amino group in the polyaspartic acid ester resin is 1.05-1.15: 1.
Preferably, the prepolymerization time of the polyurea prepolymer is 0-20 min.
Preferably, the diisocyanate is one or more of hexamethylene diisocyanate, diphenylmethane diisocyanate and isophorone diisocyanate.
Preferably, the silane coupling agent is one or more of a disiloxane-based coupling agent or a trisiloxane-based coupling agent containing amino functional groups.
Preferably, the disiloxane coupling agents are gamma-aminopropylmethyldiethoxysilane and N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, and the trisiloxane coupling agents are gamma-aminopropyltriethoxysilane and N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane.
Preferably, the polyaspartic ester resin is one or more of F420, F524 and F220.
Preferably, the curing agent is HDI trimer or a semi-prepolymer of reaction of diisocyanate and amino-terminated polyether or hydroxyl-terminated polyether.
It is a second object of the present invention to provide a silicone-modified polyurea material prepared according to the above process.
It is a third object of the present invention to provide the use of the above-described silicone-modified polyurea material in mountain reinforcement and foundation reinforcement.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the amino functional group on the silane coupling agent reacts with diisocyanate and is connected to the secondary amino group of the polyaspartic ester resin, so that the polyurea prepolymer is modified, and the siloxane group is introduced into the polyurea molecule, so that the adhesive force of the polyurea prepolymer to a base material can be further improved, and the polyurea prepolymer has potential application in mountain reinforcement and foundation reinforcement.
Drawings
FIG. 1 is a graph of die dimensions in a test of tensile strength versus elongation at break;
FIG. 2 is a graph of the mechanical properties of the silicone-modified polyurea materials prepared in examples 1-4;
FIG. 3 is a graph of the mechanical properties of the silicone-modified polyurea materials prepared in examples 4-10;
FIG. 4 is an infrared spectrum of each raw material, wherein FIG. 4A is an infrared spectrum of hexamethylene diisocyanate, FIG. 4B is an infrared spectrum of polyaspartic ester resin, FIG. 4C is an infrared spectrum of HT-100, and FIG. 4D is an infrared spectrum of KH 902;
FIG. 5 is an infrared spectrum, wherein FIG. 5A is an infrared spectrum of a silicone-free modified polyurea material in comparative example 1, and FIG. 5B is an infrared spectrum of a silicone-modified polyurea material in example 4.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, polyaspartic acid ester resin F420 was used in place of Bayer NH1420, polyaspartic acid ester resin F524 was used in place of Bayer XP7068, and polyaspartic acid ester resin F220 was used in place of Bayer NH1220, and the inert gas was nitrogen. Furthermore, KH550 represents γ -aminopropyltriethoxysilane, KH902 represents γ -aminopropylmethyldiethoxysilane, KH792 represents N- (. beta. -aminoethyl) - γ -aminopropyltrimethoxysilane, KH602 represents N- (. beta. -aminoethyl) - γ -aminopropylmethyldimethoxysilane, in the present invention, the HDI trimer is HT-100, and the semiprepolymer in which diisocyanate is reacted with amino-or hydroxy-terminated polyether is GB 805B-100.
Example 1
Stirring 30g of polyaspartic acid ester resin F420 and 0.9152g of Hexamethylene Diisocyanate (HDI) under a nitrogen atmosphere to perform prepolymerization for 10min, wherein the molar ratio of isocyanate in HDI to amino groups in F420 is 0.1: 1; 0.1105gKH550 is added, wherein the molar ratio of KH550 to HDI is 1:10, after stirring for 2h, the siloxane modified polyaspartic acid ester resin (marked as component B) is obtained, HT-100 is marked as component A, and the molar ratio of isocyanic acid radical in component A to amino group in component B is 1.06: 1 (namely the isocyanic acid index R is 1.06), weighing 18g of the component A, mixing the component A and the component B, quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the siloxane modified polyurea material.
Example 2
Stirring 30g of polyaspartic acid ester resin F420 and 0.9152g of HDI under a nitrogen atmosphere to perform prepolymerization for 10min, wherein the molar ratio of isocyanate in HDI to amino group in F420 is 0.1: 1; then 0.1112gKH792 is added, wherein the molar ratio of KH792 to HDI is 1:10, and after stirring for 2h, the siloxane modified polyaspartic acid ester resin, namely the component B is obtained; and (3) recording HT-100 as a component A, weighing 18g of the component A according to the R value of 1.06, mixing the component A and the component B, quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the siloxane modified polyurea material.
Example 3
Stirring 30g of polyaspartic acid ester resin F420 and 0.9152g of HDI under a nitrogen atmosphere to perform prepolymerization for 10min, wherein the molar ratio of isocyanate in HDI to amino group in F420 is 0.1: 1; adding 0.1032gKH602, wherein the molar ratio of KH602 to HDI is 1:10, stirring for 2h to obtain siloxane modified polyaspartic acid ester resin, namely component B; and (3) recording HT-100 as a component A, weighing 18g of the component A according to the R value of 1.06, mixing the component A and the component B, quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the siloxane modified polyurea material.
Example 4
Stirring 30g of polyaspartic acid ester resin F420 and 0.9152g of HDI under a nitrogen atmosphere to perform prepolymerization for 10min, wherein the molar ratio of isocyanate in the HDI to amino groups in the F420 is 0.1: 1; then adding 0.1gKH902, wherein the molar ratio of KH902 to HDI is 1:10, stirring for 2h to obtain siloxane modified polyaspartic acid ester resin, namely a component B; and (3) recording HT-100 as a component A, weighing 18g of the component A according to the R value of 1.06, mixing the component A and the component B, quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the siloxane modified polyurea material.
Example 5
The same procedure as in example 4 was followed, except that the prepolymerization time was 0 min.
Example 6
The same procedure as in example 4 was followed, except that the prepolymerization time was 5 min.
Example 7
The same procedure as in example 4 was followed, except that the prepolymerization time was 8 min.
Example 8
The same procedure as in example 4 was followed, except that the prepolymerization time was 12 min.
Example 9
The same procedure as in example 4 was followed, except that the prepolymerization time was 15 min.
Example 10
The same procedure as in example 4 was followed, except that the prepolymerization time was 20 min.
Example 11
The same procedure as in example 4 was followed, except that 1.0314g of KH902 was added, the molar ratio of KH902 to HDI was 1:1, and the amount of component A added was the same, except that the R value was 1.114.
Example 12
The procedure was as in example 4 except that 0.2063g of KH902 was added, the molar ratio of KH902 to HDI was 1:5, and the amount of component A added was constant but the R value was 1.07.
Example 13
The procedure was as in example 4 except that 0.0688g of KH902 was added, the molar ratio of KH902 to HDI was 1:15, and the amount of component A added was constant but the R value was 1.06.
Example 14
The procedure was as in example 4 except that 0.06g of KH902 was added, wherein the molar ratio of KH902 to HDI was 1:17, and the amount of component A added was constant but the R value was 1.06.
Example 15
The same procedure as in example 4 was followed, except that 0.043g of KH902 was added, wherein the molar ratio of KH902 to HDI was 1:23, and the amount of component A added was not changed, but the R value was 1.06.
Example 16
Stirring 30g of polyaspartic acid ester resin F524 and 0.7682g of HDI under a nitrogen atmosphere to perform prepolymerization for 10min, wherein the molar ratio of isocyanate in HDI to amino groups in F524 is 0.1: 1; 0.0382gKH902 was added, wherein the molar ratio of KH902 to HDI was 1:23, and after stirring for 2 hours, a siloxane-modified polyaspartic acid ester resin, component B, was obtained. Marking HT-100 as a component A, weighing 15.7211g of the component A according to the R value of 1.06, mixing the component A and the component B, quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, and curing and molding to obtain the siloxane modified polyurea material.
Example 17
Stirring 30g of polyaspartic acid ester resin F220 and 1.1022g of HDI under a nitrogen atmosphere to perform prepolymerization for 0min, wherein the molar ratio of isocyanate in HDI to amino group in F220 is 0.1: 1; 0.0544gKH902 was added, wherein the molar ratio of KH902 to HDI was 1:23, and after stirring for 2 hours, a siloxane-modified polyaspartic acid ester resin, component B, was obtained. Marking HT-100 as a component A, weighing 23.9212g of the component A according to the R value of 1.06, mixing the component A and the component B, quickly stirring for 0.2min, pouring into a polytetrafluoroethylene mold, and curing and molding to obtain the siloxane modified polyurea material.
Example 18
The experimental procedure of example 15 was followed except that the A component was diisocyanate group-containing prepolymer GB805B-100, and 38.0785g of the A component was weighed out in accordance with the R value of 1.06.
Example 19
30g of polyaspartate resin F420 and 1.8303g of HDI were stirred under nitrogen atmosphere to be prepolymerized for 10min, wherein the molar ratio of isocyanate group in HDI to amino group in F420 was 0.2, and then 0.0904gKH902, wherein the molar ratio of KH902 to HDI was 1:23, and stirred for 2 hours to obtain a siloxane-modified polyaspartate resin, component B. And the component A is prepared by marking HT-100 as the component A, weighing 17.94g of the component A according to the R value of 1.06, mixing the component A and the component B, quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, and curing and molding to obtain the siloxane modified polyurea material.
Example 20
30g of polyaspartic acid ester resin F420 and 2.7455g of HDI were stirred under a nitrogen atmosphere to be prepolymerized for 10min, wherein the molar ratio of isocyanate group in HDI to amino group in F420 was 0.3, and 0.1356gKH902 was added thereto, wherein the molar ratio of KH902 to HDI was 1:23, and after stirring for 2 hours, a B component was obtained. And the component A is HT-100, 17.90g of the component A is weighed according to the R value of 1.06, the component A and the component B are mixed, quickly stirred for 2min, poured into a polytetrafluoroethylene mold, and cured and molded to obtain the siloxane modified polyurea material.
Example 21
Stirring 30g of polyaspartic acid ester resin F420 and 1.3538g of diphenyl dimethylene diisocyanate (MDI) under a nitrogen atmosphere to perform prepolymerization for 10min, wherein the molar ratio of isocyanate in MDI to amino groups in F420 is 0.1: 1; then adding 0.1gKH902, wherein the molar ratio of KH902 to MDI is 1:10, stirring for 0.5h to obtain siloxane modified polyaspartic ester resin, namely a component B; and (3) recording HT-100 as a component A, weighing 18g of the component A according to the R value of 1.06, mixing the component A and the component B, quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the siloxane modified polyurea material.
Example 22
Stirring 30g of polyaspartic ester resin F420 and 1.2022g of isophorone diisocyanate (IPDI) under a nitrogen atmosphere to perform prepolymerization for 10min, wherein the molar ratio of isocyanate in IPDI to amino groups in F420 is 0.1: 1; then adding 0.1gKH902, wherein the molar ratio of KH902 to IPDI is 1:10, stirring for 4h to obtain siloxane modified polyaspartic acid ester resin, namely component B; and (3) recording HT-100 as a component A, weighing 18g of the component A according to the R value of 1.06, mixing the component A and the component B, quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the siloxane modified polyurea material.
Example 23
Stirring 15g of polyaspartic acid ester resin F420, 15g of polyaspartic acid ester resin F524 and 0.8421g of HDI under a nitrogen atmosphere to pre-polymerize the resin, wherein the pre-polymerization time is 10min, and the molar ratio of isocyanate in the HDI to amino groups in the F420 is 0.1: 1; adding 0.0952gKH902, wherein the molar ratio of KH902 to HDI is 1:10, stirring for 2h to obtain siloxane modified polyaspartic acid ester resin, namely component B; marking HT-100 as a component A, weighing 17.0311gA according to the R value of 1.06, mixing the component A and the component B, quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the siloxane modified polyurea material.
Example 24
Stirring 30g of polyaspartic acid ester resin F420, 0.4576g of HDI and 0.6769g of MDI under a nitrogen atmosphere to pre-polymerize the resin, wherein the pre-polymerization time is 10min, and the molar ratio of isocyanate in the HDI and the MDI to amino groups in the F420 is 0.1: 1; then adding 0.1gKH902, wherein the molar ratio of KH902 to HDI is 1:10, stirring for 2h to obtain siloxane modified polyaspartic acid ester resin, namely a component B; and (3) recording HT-100 as a component A, weighing 18g of the component A according to the R value of 1.06, mixing the component A and the component B, quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the siloxane modified polyurea material.
Example 25
Stirring 30g of polyaspartic acid ester resin F420 and 0.9152g of HDI under a vacuum condition to perform prepolymerization for 10min, wherein the molar ratio of isocyanate in the HDI to amino groups in the F420 is 0.1: 1; then adding silane coupling agents which are 0.05gKH902 and 0.0556g KH792, wherein the molar ratio of the silane coupling agents to the HDI is 1:10, and stirring for 2h to obtain siloxane modified polyaspartic acid ester resin, namely a component B; and (3) recording HT-100 as a component A, weighing 18g of the component A according to the R value of 1.06, mixing the component A and the component B, quickly stirring for 2min, pouring into a polytetrafluoroethylene mold, standing, curing and molding to obtain the siloxane modified polyurea material.
Comparative example 1
The same procedure as in example 4 was followed except that no silane coupling agent was added to the B-side, the A-side was 19.8224gHT-100, and the R-value was 1.05.
Comparative example 2
The procedure of example 18 was repeated, except that no silane coupling agent was added to the component B, the component A was GB805B-100, and 38.1685g of the component A was weighed out in accordance with the R value of 1.06.
The performance result of the siloxane modified polyurea material is represented by an infrared test and a mechanical test,
infrared test, the test conditions are as follows: wave number range of 400cm-1-4000cm-1Resolution of 4cm-1。
Test of tensile strength and elongation at break: according to GB/T528-2009, a sample is made into a dumbbell type standard sample bar by using a polytetrafluoroethylene mould, the size of the mould is shown in figure 1, the total length L is 150mm, the distance between clamps is 115mm, and the scale distance L is050mm, width d of test portion0The test is carried out by adopting an electronic universal tensile tester with the loading speed set to be 50mm/min and the depth set to be 4mm, 3 sample bars are tested on the same sample, and the average value of the data of the 3 samples is taken during calculation.
The tensile strength was calculated according to equation 1:
wherein σ is tensile strength in MPa, P is breaking load or yield load in N, m is specimen test zone width in mm, and N is specimen test zone thickness in mm.
Elongation at break was calculated according to equation 2:
epsilon is elongation at break (%), Go is the initial gauge length of the sample in mm, and G is the distance between gauge lines at the time of breaking of the sample in mm.
And (3) testing the adhesive force: the measurement is carried out by the pull-open method described in GB/T5210-2006. Mixing the A component and the B component of the prepared siloxane modified polyurea material, quickly stirring for 2min, coating the mixture on the surface of a polished cement mortar test block (40 x 10mm), curing for 24h, then jointing a spindle test column with the diameter of 20mm with the measured coating surface by using special mixed glue, after the jointing surface is completely solidified (about 24h), cutting the jointing surface of the test column and the coating outside the test block by using a cutter, and carrying out adhesion test by using an adhesion tester (model: BGD 500/S).
First, mechanical property
TABLE 1 mechanical Properties data for the Silicone-modified polyurea materials prepared in examples 1-4
| Examples | Silane coupling agent | Average displacement/mm | Maximum force/N | Tensile strength/MPa | Elongation at break/% |
| Example 1 | KH550 | 5.349 | 1026.490 | 25.667 | 10.698 |
| Example 2 | KH792 | 5.874 | 1338.000 | 33.452 | 11.748 |
| Example 3 | KH602 | 6.114 | 1127.101 | 28.178 | 12.228 |
| Example 4 | KH902 | 9.652 | 1673.000 | 41.858 | 19.304 |
As can be seen from Table 1 and FIG. 2, the modification effect of the silane coupling agent KH902 is the best, and the tensile strength and elongation at break of the silicone modified polyurea material are 41.858MPa and 19.304%, respectively, which are the highest values.
TABLE 2 mechanical Properties data for the Silicone-modified polyurea materials prepared in examples 4-10
| Examples | Prepolymerization time/min | Tensile strength/MPa | Elongation at break/% |
| Example 5 | 0 | 33.235 | 11.326 |
| Example 6 | 5 | 34.215 | 13.966 |
| Example 7 | 8 | 40.122 | 18.528 |
| Example 4 | 10 | 41.858 | 19.304 |
| Example 8 | 12 | 44.957 | 25.128 |
| Example 9 | 15 | 40.314 | 14.798 |
| Example 10 | 20 | 34.858 | 14.664 |
As can be seen from table 2 and fig. 3, as the prepolymerization time of HDI and polyaspartic ester resin is changed, the mechanical properties of the siloxane-modified polyurea material are increased and then decreased, because the reaction speed of the terminal amino group and HDI is fast, two isocyanate groups of HDI are consumed by siloxane to form low molecular weight substance, which reduces the prepolymerization degree between polyaspartic ester resin and HDI and increases the amount of short molecular chain prepolymer; when the prepolymerization time is longer, more HDI reacts with the polyaspartic acid ester resin, so that more KH902 residues are remained, and in the subsequent curing process, the HDI reacts with the curing agent to produce more oligomers, so that the crosslinking degree of the material is reduced, and the mechanical property of the obtained siloxane modified polyurea material is reduced
TABLE 3 mechanical Properties data for the Silicone-modified polyurea materials prepared in examples 11-15
| Examples | KH902 addition (g) | Tensile strength/MPa | Elongation at break/% |
| Example 11 | 1.0314 | 35.373 | 14.266 |
| Example 12 | 0.2063 | 35.278 | 11.854 |
| Example 13 | 0.0688 | 47.265 | 22.616 |
| Example 14 | 0.06 | 51.572 | 26.982 |
| Example 15 | 0.043 | 54.753 | 28.806 |
As can be seen from Table 3, as the amount of KH902 added increases, the mechanical properties of the silicone-modified polyurea material increase first and then decrease, and the principle is the same as that of the excessive KH902 which reacts with the curing agent first to produce more oligomers during the subsequent curing process, so that the crosslinking degree of the material decreases.
TABLE 4 mechanical Properties data for the Silicone-modified polyurea materials prepared in examples 16-17
| Examples | Kind of resin | Tensile strength/MPa | Elongation at break/% |
| Example 16 | F524 | 24.520 | 14.018 |
| Example 17 | F220 | 32.303 | 16.667 |
When the resin types are F524 and F220, the siloxane-modified polyurea material still has better tensile strength and elongation at break.
TABLE 5 mechanical Properties data for the Silicone-modified polyurea materials prepared in examples 18 and 4
| Examples | Type of component A curing agent | Tensile strength/MPa | Elongation at break/% |
| Example 18 | GB805B-100 | 9.186 | 181.234 |
| Example 4 | HT-100 | 41.858 | 19.304 |
As can be seen from Table 5, the tensile strength of the silicone-modified polyurea material obtained from the HT-100 curing agent is much higher than that of the silicone-modified polyurea material obtained from the GB805B-100 curing agent, but the elongation at break of the silicone-modified polyurea material obtained from the GB805B-100 curing agent is higher than that of the silicone-modified polyurea material obtained from the HT-100 curing agent, and the main reason is that GB805B-100 is a diisocyanate prepolymer, and only linear polymers are generated.
TABLE 6 mechanical Properties data for the Silicone-modified polyurea materials prepared in example 4 and examples 19-20
As can be seen from the data in Table 6, as the molar ratio of prepolymerized NCO/NH was increased (HDI content was increased), the mechanical properties of the polyurea obtained became worse, and when R was 0.3, both tensile strength and elongation at break were reduced by 50%. Indicating that excess HDI will form more low molecular weight prepolymer with the siloxane coupling agent, resulting in a reduction in the mechanical properties of the material.
TABLE 7 mechanical Properties data for the Silicone-modified polyurea materials prepared in example 4 and examples 21-22
| Examples | Type of pre-polymerization curing agent for component B | Tensile strength/MPa | Elongation at break/% |
| Example 4 | HDI | 41.858 | 19.304 |
| Example 21 | MDI | 13.655 | 6.745 |
| Example 22 | IPDI | 37.568 | 15.868 |
As can be seen from Table 7, when the curing agent is HDI, the mechanical properties of the silicone-modified polyurea material are enhanced.
TABLE 8 mechanical Properties data for the Silicone-modified polyurea materials prepared in examples 23-25
| Examples | Tensile strength/MPa | Elongation at break/% |
| Example 23 | 32.097 | 16.953 |
| Example 24 | 29.865 | 14.045 |
| Example 25 | 37.857 | 15.571 |
TABLE 9 mechanical Property data for the polyurea materials prepared in comparative examples 1-2
| Examples | Tensile strength/MPa | Elongation at break/% |
| Comparative example 1 | 51.282 | 23.806 |
| Comparative example 2 | 8.272 | 178.254 |
Second, infrared test results
FIG. 4 is an infrared spectrum of each raw material, and FIG. 4A is an infrared spectrum of hexamethylene diisocyanate of 2261cm-1Is an extension vibration peak of NCO group; FIG. 4B is an infrared spectrum of a polyaspartic acid ester resin of 3356cm-1The position is an imino-NH stretching vibration peak; FIG. 4C is an infrared spectrum of HT-100 at 2265cm-1Is an extension vibration peak of NCO group; FIG. 4D is an infrared spectrum of KH902 at 940cm-1Is SiOC2H5Stretching vibration peak of the radical; FIGS. 5A and 5B are infrared spectra of a non-silicone-modified polyurea material (i.e., a pure polyurea) in comparative example 1 and a silicone-modified polyurea material in example 4, respectively, 2265cm in FIG. 5A-1And 2250cm in FIG. 5B-1Stretching vibration peak of NCO group, 3350cm-1Is located at the peak of imino (-NH) stretching vibration, combined to 1580cm-1The stretching vibration peak of the urea carbonyl CO appeared nearby can confirm that urea-based structures are generated in the polyurea prepolymer and the siloxane modified polyurea material. 940cm in FIG. 5B-1In the form of Si-O-C2H5The stretching vibration absorption peak of the group indicates that the silane coupling agent KH902 is successfully connected to the polyurea molecule.
Adhesive force of siloxane modified polyurea material and cement mortar
TABLE 10 adhesion of Silicone-modified polyurea materials to Cement mortars
| Adhesion force/MPa of siloxane modified polyurea material and cement mortar | |
| Example 1 | 4.92 |
| Example 2 | 5.08 |
| Example 3 | 4.81 |
| Example 4 | 4.53 |
| Example 11 | 5.20 |
| Example 15 | 3.98 |
| Example 18 | 3.77 |
| Example 22 | 4.28 |
| Example 25 | 4.89 |
| Comparative example 1 | 3.57 |
| Comparative example 2 | 3.23 |
After the modification is carried out by the silane coupling agent, the adhesive force of the obtained siloxane modified polyurea material and the cement mortar is obviously superior to that of the siloxane-free modified polyurea material and the cement mortar.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (9)
1. A preparation method of a siloxane modified polyurea material is characterized by comprising the following steps:
under inert gas or vacuum, firstly stirring and reacting the polyaspartic ester resin with diisocyanate to pre-polymerize the resin, then adding a silane coupling agent, and stirring and reacting for 0.5-4 h to obtain siloxane modified polyaspartic ester resin;
adding a curing agent containing two or more isocyanate groups into the siloxane modified polyaspartic ester resin, stirring for 0.2-2 min, uniformly mixing, and curing and forming to obtain a siloxane modified polyurea material;
wherein in the prepolymerization reaction, the molar ratio of the isocyanic acid radical in the diisocyanate to the amino group in the polyaspartic acid ester resin is 0.1-0.3: 1, and the molar ratio of the silane coupling agent to the diisocyanate is 1: 1-23;
the molar ratio of the isocyanic acid radical in the curing agent to the amino group in the polyaspartic acid ester resin is 1.05-1.15: 1.
2. The method for preparing the silicone-modified polyurea material according to claim 1, wherein the prepolymerization time of the polyurea prepolymer is 0-20 min.
3. The method of claim 1, wherein the diisocyanate is one or more of hexamethylene diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate.
4. The method of claim 1, wherein the silane coupling agent is one or more of a disiloxane-based coupling agent or a trisiloxane-based coupling agent having amino functional groups.
5. The method as claimed in claim 4, wherein the disiloxane coupling agents are γ -aminopropylmethyldiethoxysilane and N- (β -aminoethyl) - γ -aminopropylmethyldimethoxysilane, and the trisiloxane coupling agents are γ -aminopropyltriethoxysilane and N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane.
6. The method of claim 1, wherein the polyaspartate resin is one or more of F420, F524, and F220.
7. The method of claim 1, wherein the curing agent is HDI trimer or a semi-prepolymer of a reaction of diisocyanate and amine-terminated polyether or hydroxyl-terminated polyether.
8. A silicone-modified polyurea material prepared by the process of any one of claims 1 to 7.
9. Use of a silicone-modified polyurea material according to claim 8 for mountain reinforcement and foundation reinforcement.
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