CN113717674A - Double-hardness composite polyurethane frictioning and preparation method thereof - Google Patents
Double-hardness composite polyurethane frictioning and preparation method thereof Download PDFInfo
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- CN113717674A CN113717674A CN202111108258.XA CN202111108258A CN113717674A CN 113717674 A CN113717674 A CN 113717674A CN 202111108258 A CN202111108258 A CN 202111108258A CN 113717674 A CN113717674 A CN 113717674A
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 29
- 239000004814 polyurethane Substances 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000003822 epoxy resin Substances 0.000 claims abstract description 31
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 31
- 239000012767 functional filler Substances 0.000 claims abstract description 24
- 239000003292 glue Substances 0.000 claims abstract description 24
- 229920003225 polyurethane elastomer Polymers 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 66
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 51
- 239000000178 monomer Substances 0.000 claims description 30
- 230000001070 adhesive effect Effects 0.000 claims description 28
- 239000000853 adhesive Substances 0.000 claims description 27
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 claims description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- IKWKJIWDLVYZIY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 IKWKJIWDLVYZIY-UHFFFAOYSA-M 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- DMHZDOTYAVHSEH-UHFFFAOYSA-N 1-(chloromethyl)-4-methylbenzene Chemical compound CC1=CC=C(CCl)C=C1 DMHZDOTYAVHSEH-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 5
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 5
- 229920000136 polysorbate Polymers 0.000 claims description 5
- 229920000053 polysorbate 80 Polymers 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 2
- 235000019589 hardness Nutrition 0.000 claims 5
- 150000001875 compounds Chemical class 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 230000002209 hydrophobic effect Effects 0.000 abstract description 3
- 241000894006 Bacteria Species 0.000 abstract description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 2
- 230000003385 bacteriostatic effect Effects 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 125000003700 epoxy group Chemical group 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000007790 scraping Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000007639 printing Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 150000001263 acyl chlorides Chemical group 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 2
- CNARCWANHGVQQW-UHFFFAOYSA-N C(C)#N.BrCCCCCCCCCCCC Chemical compound C(C)#N.BrCCCCCCCCCCCC CNARCWANHGVQQW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229910000086 alane Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Images
Classifications
-
- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41F—PRINTING MACHINES OR PRESSES
- B41F15/00—Screen printers
- B41F15/14—Details
- B41F15/40—Inking units
- B41F15/42—Inking units comprising squeegees or doctors
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a dual-hardness composite polyurethane frictioning and a preparation method thereof, belonging to the technical field of polyurethane frictioning, the dual-hardness composite polyurethane frictioning comprises a low-hardness polyurethane elastomer layer with the hardness of 45-60A and a high-hardness polyurethane elastomer layer with the hardness of 65-75A, wherein the high-hardness layer and the low-hardness layer are connected by bonding glue, and the two layers of polyurethane elastomers are connected and then cut and formed to finish the preparation, wherein the bonding glue is made of epoxy resin modified by functional filler, the functional filler reacts with hydroxyl and epoxy groups of the epoxy resin to form cross-linking, so that the bonding glue has better cohesiveness, simultaneously has good antibacterial and bacteriostatic properties, is provided with long-chain alkyl groups, further enhances the hydrophobic property, can effectively prevent the corrosion of water and bacteria, has better bonding effect, and is applied to the bonding of the two polyurethane elastomers with the hardness, the fastness is good, can not split easily.
Description
Technical Field
The invention relates to the technical field of polyurethane frictioning, in particular to double-hardness composite polyurethane frictioning and a preparation method thereof.
Background
The scraping glue is also called glue scraping, also called silk screen glue scraping, and is an adhesive tape which takes an elastic material as a raw material and is used in the silk screen printing process. The squeegee with different cross-sectional shapes can be selected according to the characteristics of the printing stock for screen printing, the precision requirement of the printing pattern and the difference of the printing modes. The cross section of the frictioning generally has a right angle shape, a sharp angle shape, an arc shape and the like.
The scraping glue usually uses polyurethane as a raw material, the hardness of the scraping glue refers to the hardness of the surface of the scraping glue, the hardness is usually expressed by Shore hardness (A), the scraping glue is 55 degrees, 60 degrees, 65 degrees, 70 degrees, 75 degrees, 80 degrees and 85 degrees, the scraping glue with different hardness is suitable for different ink printing, the scraping glue at the present stage generally only has single hardness and can only be suitable for the ink with proper hardness, the use range is limited, but the bonding strength between polyurethane elastomers with different hardness is insufficient, the risk of separation is caused easily.
Disclosure of Invention
The invention aims to provide a double-hardness composite polyurethane frictioning and a preparation method thereof, which are used for solving the problems in the background technology.
The purpose of the invention can be realized by the following technical scheme:
the dual-hardness composite polyurethane frictioning comprises a low-hardness polyurethane elastomer layer with the hardness of 45-60A and a high-hardness polyurethane elastomer layer with the hardness of 65-75A, wherein the high-hardness layer and the low-hardness layer are connected through bonding glue.
The double-hardness composite polyurethane frictioning is prepared by the following steps:
and (3) bonding the low-hardness polyurethane elastomer layer with the hardness of 45-60A and the high-hardness polyurethane elastomer layer with the hardness of 65-75A together by using a bonding adhesive, and cutting and forming to obtain the double-hardness composite polyurethane frictioning.
As a further scheme of the invention: the low hardness layer is designated as layer A and the high hardness layer is designated as layer B.
As a further scheme of the invention: the adhesive is prepared by the following steps:
the method comprises the following steps: weighing the following raw materials in parts by weight: 98-118 parts of modified epoxy resin, 801.5-3.5 parts of tween and 0.07-0.09 part of butyl triphenyl phosphonium bromide;
step two: adding the modified epoxy resin into a stirring kettle, adding Tween 80, stirring at the temperature of 50 ℃ and the rotation speed of 500r/min for 20min, adding butyl triphenyl phosphonium bromide, stirring at the temperature of 50 ℃ for 10min, heating to 90-110 ℃, reacting for 3h, and cooling to 50-60 ℃ after the reaction is finished to obtain the adhesive.
As a further scheme of the invention: the modified epoxy resin is prepared by the following steps: adding the functional filler into an ethanol aqueous solution which is 40 times of the functional filler in mass and has the mass fraction of 90%, stirring, adding the epoxy resin, stirring and reacting for 1h at room temperature, washing for 3 times by using absolute ethanol, filtering and freeze-drying to obtain modified epoxy resin; wherein the dosage ratio of the functional filler to the epoxy resin is 1 g: 10 g.
As a further scheme of the invention: the functional filler is prepared by the following steps:
step S1: adding imidazole and solid sodium hydroxide into a flask, then adding acetonitrile, stirring for 15min, introducing nitrogen, then ultrasonically oscillating for 15min, stirring for 5min, then adding an acetonitrile solution of bromododecane, and stirring and reacting for 10-12h at the temperature of 60 ℃ to obtain an intermediate 1; wherein the dosage ratio of the imidazole, sodium hydroxide, acetonitrile and bromododecane acetonitrile solution is 0.5 mol: 0.7 mol: 120mL of: 15 mL; the acetonitrile solution of bromododecane is prepared from bromododecane and acetonitrile according to the dosage ratio of 0.06 mol: 15mL of the mixture is obtained;
bromododecane is substituted with a secondary amine of imidazole to make imidazole have a long-chain alkyl group, and the reaction process is as follows:
step S2: adding the intermediate 1 and chloroform into a flask, then adding p-methylbenzyl chloride and a polymerization inhibitor, stirring for 10min, then heating to 50 ℃, and continuing stirring for reaction for 9-10h to obtain an intermediate 2; wherein the dosage ratio of the intermediate 1, chloroform, p-methylbenzyl chloride and polymerization inhibitor is 0.2 mol: 100mL of: 0.22 mol: 0.01 mol; wherein the polymerization inhibitor is 2, 6-di-tert-butyl-4-methylphenol;
the chlorine of p-methyl benzyl chloride and the tertiary amine of the intermediate 1 are subjected to quaternization reaction, so that the intermediate 2 forms an imidazole quaternary ammonium salt structure, and the reaction process is as follows:
step S3: adding the intermediate 2 and deionized water into a flask for refluxing, then adding potassium permanganate for refluxing reaction for 3 hours to obtain an intermediate 3, then adding the intermediate 3 and deionized water into the flask, then adding thionyl chloride and DMF, and reacting for 4 hours at 75 ℃ to obtain a functional monomer a; wherein the molar ratio of the intermediate 2 to the potassium permanganate is 1: 1.2, the using amount ratio of the intermediate 3, the thionyl chloride and the DMF is 0.1 mol: 0.13 mol: 0.05 mL;
the methyl of the intermediate 2 is converted into acyl chloride group with high reactivity through oxidation and acylation; the reaction process is as follows:
step S4: adding 3-aminopropyltriethoxysilane into a flask filled with dichloromethane, stirring for 15min, then dropwise adding a dichloromethane solution of a functional monomer a into the flask, then adding triethylamine, and reacting for 3-4h to obtain a functional filler; wherein the dosage ratio of the 3-aminopropyltriethoxysilane, the dichloromethane solution of the functional monomer a and the triethylamine is 0.02 mol: 10mL of: 10mL of: 0.025mol, wherein the dichloromethane solution of the functional monomer a is prepared by mixing the functional monomer a and dichloromethane in a dosage ratio of 1 g: 10mL of the mixture is obtained;
reacting acyl chloride groups of the functional monomer a with amino groups of 3-aminopropyltriethoxysilane to connect the functional monomer a and a silane coupling agent together; the reaction process is as follows:
the invention provides a double-hardness composite polyurethane frictioning and a preparation method thereof. Compared with the prior art, the method has the following beneficial effects: the invention utilizes a bonding adhesive to connect polyurethane elastomer layers with two hardness to obtain the polyurethane scraping adhesive with double hardness, wherein the bonding adhesive is prepared from modified epoxy resin; the invention utilizes a functional filler modified epoxy resin, the functional filler is prepared by the reaction of a functional monomer a and silane coupling agent 3-aminopropyl triethoxysilane, wherein the functional monomer a reacts with amino of the 3-aminopropyl triethoxysilane to ensure that the functional monomer a also has exposed siloxane groups, the siloxane groups can react with hydroxyl groups and epoxy groups on the epoxy resin after hydrolysis, thereby combining functional filler molecules into the epoxy resin and forming crosslinking, the prepared adhesive has better cohesiveness, polyurethane elastomer layers on two sides are firmly combined together, the Si-O-Si structure can also improve the hydrophobic property of the epoxy resin, meanwhile, the functional monomer a is provided with a benzyl imidazole quaternary ammonium salt structure to endow the functional monomer a with good antibacterial and bacteriostatic properties, and the imidazole salt structure is also connected with long chain alkyl, the hydrophobic property of the epoxy resin is further enhanced, so that the prepared adhesive can effectively prevent water and bacteria from being corroded, has better adhesive effect, and cannot be easily separated.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic structural diagram of a dual-hardness composite polyurethane frictioning.
In the drawings, the components represented by the respective reference numerals are listed below:
1. a layer; 2. and B layer.
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.
Referring to fig. 1, a dual hardness composite polyurethane coating according to the present invention is shown, in which a layer 1 is a low hardness polyurethane elastomer layer having a hardness of 45-60A, and a layer 2 is a high hardness polyurethane elastomer layer having a hardness of 65-75A.
Example 1
Preparing a functional filler, wherein the functional filler is prepared by the following steps:
step S1: adding 0.5mol of imidazole and 0.7mol of solid sodium hydroxide into a flask, then adding 120mL of acetonitrile, stirring for 15min, introducing nitrogen, then ultrasonically oscillating for 15min, stirring for 5min, then adding 15mL of acetonitrile solution of bromododecane, and stirring and reacting for 10h at the temperature of 60 ℃ to obtain an intermediate 1; wherein, the acetonitrile solution of bromododecane is bromododecane and acetonitrile according to the dosage ratio of 0.06 mol: 15mL of the mixture is obtained;
step S2: adding 0.2mol of intermediate 1 and 100mL of chloroform into a flask, then adding 0.22mol of p-methylbenzyl chloride and 0.01mol of 2, 6-di-tert-butyl-4-methylphenol, stirring for 10min, then heating to 50 ℃, and continuing stirring for reaction for 9h to obtain an intermediate 2;
step S3: adding 0.1mol of intermediate 2 and 200mL of deionized water into a flask for refluxing, then adding 0.12mol of potassium permanganate for refluxing reaction for 3 hours to prepare an intermediate 3, then adding 0.1mol of intermediate 3 and 250mL of deionized water into the flask, then adding 0.13mol of thionyl chloride and 0.05mLDMF, and reacting for 4 hours at 75 ℃ to prepare a functional monomer a;
step S4: adding 3-aminopropyltriethoxysilane 0.2mol into a flask filled with 100mL of dichloromethane, stirring for 15min, then dropwise adding 10mL of dichloromethane solution of the functional monomer a into the flask, then adding triethylamine 0.25mol, and reacting for 3h to obtain a functional filler; wherein the dichloromethane solution of the functional monomer a is prepared by mixing the functional monomer a and dichloromethane according to the dosage ratio of 1 g: 10mL of the mixture was mixed.
Example 2
Preparing a functional filler, wherein the functional filler is prepared by the following steps:
step S1: adding 0.5mol of imidazole and 0.7mol of solid sodium hydroxide into a flask, then adding 120mL of acetonitrile, stirring for 15min, introducing nitrogen, then ultrasonically oscillating for 15min, stirring for 5min, then adding 15mL of acetonitrile solution of bromododecane, and stirring and reacting for 11h at the temperature of 60 ℃ to obtain an intermediate 1; wherein, the acetonitrile solution of bromododecane is bromododecane and acetonitrile according to the dosage ratio of 0.06 mol: 15mL of the mixture is obtained;
step S2: adding 0.2mol of intermediate 1 and 100mL of chloroform into a flask, then adding 0.22mol of p-methylbenzyl chloride and 0.01mol of 2, 6-di-tert-butyl-4-methylphenol, stirring for 10min, then heating to 50 ℃, and continuing to stir for reaction for 9.5h to obtain an intermediate 2;
step S3: adding 0.1mol of intermediate 2 and 200mL of deionized water into a flask for refluxing, then adding 0.12mol of potassium permanganate for refluxing reaction for 3 hours to prepare an intermediate 3, then adding 0.1mol of intermediate 3 and 250mL of deionized water into the flask, then adding 0.13mol of thionyl chloride and 0.05mLDMF, and reacting for 4 hours at 75 ℃ to prepare a functional monomer a;
step S4: adding 3-aminopropyltriethoxysilane 0.2mol into a flask filled with 100mL of dichloromethane, stirring for 15min, then dropwise adding 10mL of dichloromethane solution of the functional monomer a into the flask, then adding triethylamine 0.25mol, and reacting for 3.5h to obtain a functional filler; wherein the dichloromethane solution of the functional monomer a is prepared by mixing the functional monomer a and dichloromethane according to the dosage ratio of 1 g: 10mL of the mixture was mixed.
Example 3
Preparing a functional filler, wherein the functional filler is prepared by the following steps:
step S1: adding 0.5mol of imidazole and 0.7mol of solid sodium hydroxide into a flask, then adding 120mL of acetonitrile, stirring for 15min, introducing nitrogen, then ultrasonically oscillating for 15min, stirring for 5min, then adding 15mL of acetonitrile solution of bromododecane, and stirring and reacting at the temperature of 60 ℃ for 12h to obtain an intermediate 1; wherein, the acetonitrile solution of bromododecane is bromododecane and acetonitrile according to the dosage ratio of 0.06 mol: 15mL of the mixture is obtained;
step S2: adding 0.2mol of intermediate 1 and 100mL of chloroform into a flask, then adding 0.22mol of p-methylbenzyl chloride and 0.01mol of 2, 6-di-tert-butyl-4-methylphenol, stirring for 10min, then heating to 50 ℃, and continuing to stir for reaction for 10h to obtain an intermediate 2;
step S3: adding 0.1mol of intermediate 2 and 200mL of deionized water into a flask for refluxing, then adding 0.12mol of potassium permanganate for refluxing reaction for 3 hours to prepare an intermediate 3, then adding 0.1mol of intermediate 3 and 250mL of deionized water into the flask, then adding 0.13mol of thionyl chloride and 0.05mLDMF, and reacting for 4 hours at 75 ℃ to prepare a functional monomer a;
step S4: adding 3-aminopropyltriethoxysilane 0.2mol into a flask filled with 100mL of dichloromethane, stirring for 15min, then dropwise adding 10mL of dichloromethane solution of the functional monomer a into the flask, then adding triethylamine 0.25mol, and reacting for 4h to obtain a functional filler; wherein the dichloromethane solution of the functional monomer a is prepared by mixing the functional monomer a and dichloromethane according to the dosage ratio of 1 g: 10mL of the mixture was mixed.
Example 4
Preparing modified epoxy resin, wherein the modified epoxy resin is prepared by the following steps:
adding 5g of the functional filler prepared in the example 2 into 0.2kg of ethanol aqueous solution with the mass fraction of 90%, stirring, adding 50g of epoxy resin, stirring and reacting at room temperature for 1h, washing for 3 times by using absolute ethyl alcohol, filtering, and freeze-drying to obtain modified epoxy resin;
example 5
Preparing adhesive glue, wherein the adhesive glue is prepared by the following steps:
the method comprises the following steps: weighing 98 parts of modified epoxy resin prepared in example 4, 801.5 parts of tween and 0.07 part of butyl triphenyl phosphonium bromide according to parts by weight;
step two: adding the modified epoxy resin into a stirring kettle, adding Tween 80, stirring at the temperature of 50 ℃ and the rotation speed of 500r/min for 20min, adding butyl triphenyl phosphonium bromide, stirring at the temperature of 50 ℃ for 10min, heating to 90 ℃, reacting for 3h, and cooling to 50 ℃ after the reaction is finished to obtain the adhesive.
Example 6
Preparing adhesive glue, wherein the adhesive glue is prepared by the following steps:
the method comprises the following steps: weighing 108 parts of modified epoxy resin prepared in example 4, 802.5 parts of tween and 0.08 part of butyl triphenyl phosphonium bromide according to parts by weight;
step two: adding the modified epoxy resin into a stirring kettle, adding Tween 80, stirring at the temperature of 50 ℃ and the rotation speed of 500r/min for 20min, adding butyl triphenyl phosphonium bromide, stirring at the temperature of 50 ℃ for 10min, heating to 100 ℃, reacting for 3h, and cooling to 55 ℃ after the reaction is finished to obtain the adhesive.
Example 7
Preparing adhesive glue, wherein the adhesive glue is prepared by the following steps:
the method comprises the following steps: weighing 118 parts of the modified epoxy resin prepared in the embodiment 4, 803.5 parts of tween and 0.09 part of butyl triphenyl phosphonium bromide according to the parts by weight;
step two: adding the modified epoxy resin into a stirring kettle, adding Tween 80, stirring at the temperature of 50 ℃ and the rotation speed of 500r/min for 20min, adding butyl triphenyl phosphonium bromide, stirring at the temperature of 50 ℃ for 10min, heating to 110 ℃, reacting for 3h, and cooling to 60 ℃ after the reaction is finished to obtain the adhesive.
Example 8
A low-hardness polyurethane elastomer layer having a hardness of 45A and a high-hardness polyurethane elastomer layer having a hardness of 65A were bonded together using the adhesive prepared in example 6, and cut into a shape to prepare a dual-hardness composite polyurethane spread.
Example 9
A low-hardness polyurethane elastomer layer having a hardness of 55A and a high-hardness polyurethane elastomer layer having a hardness of 70A were bonded together using the adhesive prepared in example 6, and cut into a shape to prepare a dual-hardness composite polyurethane spread.
Example 10
A low-hardness polyurethane elastomer layer having a hardness of 60A and a high-hardness polyurethane elastomer layer having a hardness of 75A were bonded together using the adhesive prepared in example 6, and cut into a shape to prepare a dual-hardness composite polyurethane spread.
Comparative example 1: an adhesive glue was prepared using an unmodified epoxy resin compared to example 6;
comparative example 2: the adhesive glue prepared in comparative example 1 was used compared to comparative example 9, the rest being unchanged.
Comparative example 3: a bond paste was prepared using kh550 modified epoxy resin compared to example 6;
comparative example 4: the adhesive glue prepared in comparative example 2 was used compared to comparative example 9, the rest being unchanged.
Tensile properties and peel strength tests were carried out on the dual-hardness polyurethanes prepared in examples 8 to 10 and comparative examples 2 and 4, with respect to the adhesive, according to the measurement standards GB/T7124-2008 and GB/T2791-1995, and the results are shown in the following table:
as can be seen from the above table, examples 8 to 10 are firmly bonded and are not easily detached or damaged.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (9)
1. The utility model provides a compound polyurethane frictioning of two hardnesses which characterized in that: comprises an A layer (1) and a B layer (2), wherein the A layer (1) and the B layer (2) are connected by bonding glue;
wherein the bonding glue is prepared by the following steps:
adding the modified epoxy resin into a stirring kettle, adding Tween 80, adding butyl triphenyl phosphonium bromide after stirring, stirring at 50 ℃ for 10min, heating to 90-110 ℃, reacting for 3h, and cooling to 50-60 ℃ after the reaction is finished to obtain the adhesive.
2. The dual-hardness composite polyurethane frictioning as claimed in claim 1, wherein: the layer A (1) is a low-hardness polyurethane elastomer layer with the hardness of 45-60A, and the layer B (2) is a high-hardness polyurethane elastomer layer with the hardness of 65-75A.
3. The dual-hardness composite polyurethane frictioning as claimed in claim 1, wherein: the adhesive comprises the following raw materials in parts by weight: 98-118 parts of modified epoxy resin, 801.5-3.5 parts of tween and 0.07-0.09 part of butyl triphenyl phosphonium bromide.
4. The dual-hardness composite polyurethane frictioning as claimed in claim 1, wherein: the modified epoxy resin is prepared by the following steps:
adding the functional filler into an ethanol aqueous solution which is 40 times of the functional filler in mass and has the mass fraction of 90%, stirring, adding the epoxy resin, stirring and reacting for 1h at room temperature, washing for 3 times by using absolute ethanol, filtering and freeze-drying to obtain the modified epoxy resin.
5. The dual-hardness composite polyurethane frictioning of claim 4, wherein: the functional filler is prepared by the following steps:
adding 3-aminopropyltriethoxysilane into a flask filled with dichloromethane, stirring for 15min, then dropwise adding a dichloromethane solution of the functional monomer a into the flask, then adding triethylamine, and reacting for 3-4h to obtain the functional filler.
6. The dual-hardness composite polyurethane frictioning of claim 5, wherein: the dosage ratio of the 3-aminopropyltriethoxysilane, the dichloromethane solution of the functional monomer a and the triethylamine is 0.02 mol: 10mL of: 10mL of: 0.025mol, wherein the dichloromethane solution of the functional monomer a is prepared by mixing the functional monomer a and dichloromethane in a dosage ratio of 1 g: 10mL of the mixture was mixed.
7. The dual-hardness composite polyurethane frictioning of claim 5, wherein: the functional monomer a is prepared by the following steps:
step S1: adding imidazole and solid sodium hydroxide into a flask, then adding acetonitrile, stirring for 15min, introducing nitrogen, then ultrasonically oscillating for 15min, stirring for 5min, then adding an acetonitrile solution of bromododecane, and stirring and reacting for 10-12h at the temperature of 60 ℃ to obtain an intermediate 1;
step S2: adding the intermediate 1 and chloroform into a flask, then adding p-methylbenzyl chloride and a polymerization inhibitor, stirring for 10min, then heating to 50 ℃, and continuing stirring for reaction for 9-10h to obtain an intermediate 2;
step S3: adding the intermediate 2 and deionized water into a flask for refluxing, then adding potassium permanganate for refluxing and reacting for 3 hours to obtain an intermediate 3, then adding the intermediate 3 and deionized water into the flask, then adding thionyl chloride and DMF, and reacting for 4 hours at 75 ℃ to obtain a functional monomer a.
8. The dual-hardness composite polyurethane frictioning of claim 7, wherein: the polymerization inhibitor in step S2 is 2, 6-di-tert-butyl-4-methylphenol.
9. The preparation method of the double-hardness composite polyurethane frictioning as claimed in claim 1, wherein the preparation method comprises the following steps: the method comprises the following specific steps:
and (3) bonding the low-hardness polyurethane elastomer layer with the hardness of 45-60A and the high-hardness polyurethane elastomer layer with the hardness of 65-75A together by using a bonding adhesive, and cutting and forming to obtain the double-hardness composite polyurethane frictioning.
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|---|---|---|---|---|
| CN102775948A (en) * | 2012-07-10 | 2012-11-14 | 苗根喜 | Hydrophilic epoxy resin binder and preparation method and application thereof |
| CN202809429U (en) * | 2012-07-11 | 2013-03-20 | 亿利沙材料科技有限责任公司 | Water-seepage brick containing hydrophilic epoxy resin binder |
| CN105778474A (en) * | 2014-12-22 | 2016-07-20 | 天津市富东印刷材料厂 | Polyurethane elastomer rubber scraper |
| CN213108626U (en) * | 2020-07-10 | 2021-05-04 | 深圳市安吉森电子有限公司 | Reinforced sandwich oblique-angle frictioning strip |
| CN113416028A (en) * | 2021-07-15 | 2021-09-21 | 安徽瑞联节能科技股份有限公司 | Production process of waterproof aerogel thermal insulation material |
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2021
- 2021-09-22 CN CN202111108258.XA patent/CN113717674A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775948A (en) * | 2012-07-10 | 2012-11-14 | 苗根喜 | Hydrophilic epoxy resin binder and preparation method and application thereof |
| CN202809429U (en) * | 2012-07-11 | 2013-03-20 | 亿利沙材料科技有限责任公司 | Water-seepage brick containing hydrophilic epoxy resin binder |
| CN105778474A (en) * | 2014-12-22 | 2016-07-20 | 天津市富东印刷材料厂 | Polyurethane elastomer rubber scraper |
| CN213108626U (en) * | 2020-07-10 | 2021-05-04 | 深圳市安吉森电子有限公司 | Reinforced sandwich oblique-angle frictioning strip |
| CN113416028A (en) * | 2021-07-15 | 2021-09-21 | 安徽瑞联节能科技股份有限公司 | Production process of waterproof aerogel thermal insulation material |
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