CN115340655B - Polyurethane wiper strip material and application thereof - Google Patents

Polyurethane wiper strip material and application thereof Download PDF

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Publication number
CN115340655B
CN115340655B CN202211018942.3A CN202211018942A CN115340655B CN 115340655 B CN115340655 B CN 115340655B CN 202211018942 A CN202211018942 A CN 202211018942A CN 115340655 B CN115340655 B CN 115340655B
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polyurethane
wiper strip
strip material
modified nano
polyol
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CN115340655A (en
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唐凯荣
唐亮
任林
刘晶
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Midwest Shanghai Equipment Spare Parts Co ltd
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Midwest Shanghai Equipment Spare Parts Co ltd
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    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L11/00—Machines for cleaning floors, carpets, furniture, walls, or wall coverings
    • A47L11/40—Parts or details of machines not provided for in groups A47L11/02 - A47L11/38, or not restricted to one of these groups, e.g. handles, arrangements of switches, skirts, buffers, levers
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  • Polyurethanes Or Polyureas (AREA)

Abstract

The application discloses a polyurethane material wiper strip material and application thereof, relates to the technical field of floor cleaning machine wiper strip materials, and particularly relates to the field of preparation of polyurethane material compositions. The components of the polyurethane wiper strip material comprise a polyol composition, isocyanate, a chain extender, modified nano metal oxide and a functional additive. Wherein the polyol composition comprises a polyether polyol, a polyester polyol, an alkyl hydroxy polysiloxane, and a hydroxy terminated polybutadiene; the functional additive comprises an antioxidant, silver powder and an ultraviolet absorber. The polyurethane water scraping rubber strip obtained by the prepolymer two-step process and vulcanization of the components has the advantages of low hardness, high rebound resilience, mildew resistance, bacteria resistance and yellowing resistance, and simultaneously has excellent wear resistance and water scraping working performance, and can be applied to water scraping fittings of a floor washing machine.

Description

Polyurethane wiper strip material and application thereof
Technical Field
The application relates to the technical field of floor cleaning machine wiper strip materials, in particular to the field of preparation of polyurethane material compositions.
Background
Under the background of fast pace of modern life, the traditional manual mop has low ground cleaning mode efficiency and high cost, and has large physical labor burden for staff. The cleaning mode of the floor cleaning machine is quicker and more effective, is particularly suitable for cleaning large-area hard floors, and does not require excessive physical labor of staff.
The floor washing machine is also called a floor washing machine and a floor washing and sucking machine, and replaces manual cleaning by machinery. The cleaning device can clean the hard ground and can treat sewage generated after cleaning by using the water scraping adhesive tape and the water absorbing rake, and is widely applied to places with wide hard ground such as supermarkets, markets, wharfs, airports, workshops, warehouses, schools, hospitals, restaurants, selling places and the like. The wiper rubber strip is used as a part for wiping, abrasion is easy to be caused by long-time contact friction with the hard ground, the severe environment of partial heavy oil stains is easy to cause mildew, yellowing and cracking damage, the wiper rubber strip after abrasion directly reduces the wiping effect of the wiper rubber strip on the hard ground, and even the residual of sewage is caused, so that the cleanliness of the ground is affected.
At present, the wiper strips on the market can be divided into two categories of rubber and polyurethane according to materials. The wiper rubber strip made of common natural rubber has good elasticity, is suitable for smooth ground environments such as markets, offices and the like, and has relatively low price, but has the defects of oil resistance, quicker abrasion, incomplete sewage recovery and shorter service life. In order to reduce the degree of friction and increase the abrasion resistance of the wiper strip, there are disclosed modification methods for rubber, such as impregnation, lamination, physical treatments such as kneading of lubricant and resin, and chemical treatments of various drugs such as acid, alkali, halogen, and the like. Among them, halogen treatments such as chlorination treatments are common. However, the initial friction coefficient can be reduced by the above-mentioned chlorination treatment, but there is a problem that the friction coefficient is increased and the sliding property is deteriorated after long-term use. In addition, wiper strips made of synthetic rubber having a saturated polymer chain structure, such as ethylene-propylene-diene rubber (EPDM), cannot be hardened on the surface by halogenation due to the saturated polymer chain.
The polyurethane wiper strip has the advantages of low hardness, tear resistance, acid and alkali resistance, oil resistance, strong wiping performance, difficult abrasion and the like. Among these, some one-component polyether or polyester polyurethane wiper strips have excellent mechanical strength and elasticity, very good adhesion and abrasion resistance, and a simple process of extrusion from the melt, but have yet to be improved in terms of uv resistance, yellowing resistance, weather resistance and low-temperature resilience.
Disclosure of Invention
In order to solve the problems in the prior art, the application discloses a polyurethane material wiper strip material with low hardness, high rebound and good wiper effect and application thereof, and the technical scheme is as follows:
the raw materials of the polyurethane wiper strip material comprise a polyol composition, a polyisocyanate composition, a chain extender, a modified nano metal oxide and a functional additive; wherein the polyol composition comprises a polyether polyol, a polyester polyol, an alkyl hydroxy polysiloxane, and a hydroxy terminated polybutadiene; the chain extender is 1, 4-Butanediol (BDO) or 1, 6-Hexanediol (HDO); the functional additive comprises an antioxidant, silver powder and an ultraviolet absorber.
As a further scheme of the application, the polyether polyol is one or more of polyoxypropylene-polyoxyethylene dihydric alcohol and polytetrahydrofuran ether glycol (PTMG) with the number average molecular weight of 500-3000 g/mol. "xx-hydroxy polyether polyol" is understood to be a nominal xx-hydroxy polyether polyol. In practice, the nominal hydroxyl number (hydroxyl number) deviates because various side reactions during the polyol synthesis can lead to hydroxyl levels that are actually below the nominal assumption. The polyether polyol is used as a soft segment unit in the polyurethane wiper strip material, has main influence on rebound resilience and water resistance of the wiper strip material, because when the hardness of the polyurethane elastomer is close, the rebound resilience of the polyether soft segment is higher than that of the polyester soft segment, and the root cause is that the ether group space bit group in the polyether is small, and the flexibility of the molecular chain segment is good. Whereas polyoxypropylene-polyoxyethylene glycol and polytetrahydrofuran ether glycol (PTMG) are typical polyether glycols, the segments of which are quite soft. It is known to those skilled in the art that as the relative molecular mass of the soft segment increases, the resilience of the polyurethane increases as well, since as the relative molecular mass increases, the number of conformations of the molecule increases and the flexibility of the molecular chain increases. However, when the relative molecular weight exceeds 3000, the rebound resilience of polyurethane is more directly related to the soft segment content, and too high a soft segment molecular weight tends to cause a decrease in hardness and abrasion resistance of polyurethane wiper strips.
As a further aspect of the application, the polyester polyol is prepared as follows: vacuumizing a reaction kettle, introducing nitrogen, and sequentially adding phthalic anhydride, diethylene glycol, 1, 6-hexanediol, trimethylolpropane and a catalyst into the reaction kettle, wherein the phthalic anhydride is prepared by the following components in parts by weight: diethylene glycol: 1, 6-hexanediol: trimethylolpropane=51-54:10-25:12-25:10-20. Stirring and heating to 140-150 ℃, preserving heat for 1-3h, removing water generated during melt polycondensation, heating to 170-180 ℃, preserving heat for 6-10h, and ending the reaction when the acid value is detected to be lower than 3mg KOH/g. The polyester polyol is formed by melt polycondensation of dibasic acid anhydride, dihydric alcohol and polyhydric alcohol in a nitrogen atmosphere in a reaction kettle. As known by the person skilled in the art, the state of introducing nitrogen into the reaction kettle is always kept, and two main functions are that firstly, residual oxygen in the reaction system is removed to avoid color deepening, and on the other hand, moisture generated by the reaction is also brought out, so that the polymerization reaction is promoted to be carried out in the expected direction. In addition, phthalic anhydride provides a hard polyester segment due to certain structural rigidity, so that the final product has certain hardness and wear resistance, and the carbon chains of diethylene glycol, 1, 6-hexanediol and trimethylolpropane are longer, so that a soft polyester segment can be provided. The soft-hard block polyester structure is favorable for forming a microphase separation structure of polyurethane, and improves the comprehensive mechanical property, the coordination modulus and the rebound resilience of the material. Furthermore, it is known to the person skilled in the art that the catalysts used for the polycondensation reaction are generally organometallic compounds, in particular tin, zinc, bismuth, titanium, zirconium, aluminum. Examples of such catalysts are tin (II) acetate, tin (II) octoate and tin (II) laurate, and dialkyltin (IV) salts of organic carboxylic acids, such catalysts being dibutyltin diacetate and dibutyltin dilaurate. The catalyst used in the preparation process of the polyester polyol is monobutyl tin oxide.
As a further scheme of the application, the structural general formula of the alkyl hydroxyl polysiloxane is as follows:
wherein n is an integer between 5 and 20, and a+b is an integer between 4 and 10.
The alkyl hydroxyl polysiloxane is mainly used for further improving the ultraviolet resistance, yellowing resistance, weather resistance and low-temperature rebound performance of the polyurethane wiper strip. The silicon-methyl structure in polysiloxane increases the intermolecular distance, so that the macromolecular chain is easy to orient along the acting force direction, the sub-microcosmic phase separation of the soft and hard chain segments is enhanced, the structural regularity and the tensile strength of the aggregated state of the material are improved, and the tensile elongation is increased. However, when the n value of the polysiloxane segment unit is too large (more than 20), the mechanical properties, particularly tensile strength, of the polyurethane wiper strip material are significantly impaired, and the degree of microscopic phase separation is increased due to further incompatibility of the polysiloxane and polyether/polyester segments, and the transparency of the polyurethane wiper strip material is affected.
The alkyl hydroxyl polysiloxane can be directly purchased from the market with corresponding specification, such as corning (Corning. Co), wacker chemistry (Wacker. Co), chong Yao technology and other companies, and also can be self-made. As is familiar to those skilled in the art, the self-control process is generally a hydrosilylation addition reaction of double-ended hydrogen silicone oil with allyl polyether in the presence of a platinum catalyst.
As a further aspect of the application, the hydroxyl-terminated polybutadiene (HTPB) has a data molecular weight of 2000-4000g/mol. Polybutadiene is introduced into a polyurethane chain segment as a soft segment structural unit, has excellent hydrolysis resistance, low-temperature rebound resilience and corrosion resistance, is segmented with a polyisocyanate hard segment together with other polyether, polyester and polysiloxane soft segments, can improve the thermodynamic incompatibility of the soft segment and the hard segment, and forms a two-phase spontaneous microphase separated morphological structure, so that the mechanical property of the polyurethane material is comprehensively improved. The hydroxyl-terminated polybutadiene can be directly purchased from the market with corresponding specifications, such as from dawn chemical industry Co., ltd., ARCO, japan Caesalpinia, etc
As a further embodiment of the application, the isocyanate is an aliphatic diisocyanate, more preferably Hexamethylene Diisocyanate (HDI) or isoparaffin diisocyanate (IPDI). HDI and IPDI have better resilience and yellowing resistance than aromatic isocyanates such as Toluene Diisocyanate (TDI) and diphenylmethane diisocyanate (MDI).
As a further scheme of the application, the modified nano metal oxide is nano SiO surface-treated by a silane coupling agent 2 Or nano Al 2 O 3 The addition amount is 0.5-2.0% of the total material mass fraction. The nano metal oxide is a material with small particle size and large specific surface area, and the heat stability and ageing resistance of the material can be improved, especially the wear resistance of the material can be improved by adding the nano metal oxide into polyurethane. Nano SiO 2 Or nano Al 2 O 3 The surface has a plurality of active hydroxyl groups, and can be combined with the polyurethane main structure through Van der Waals force or covalent bond. However, such nanoparticles have a high specific surface energy, and cannot be uniformly dispersed in polyurethane, so that compatibility of a mixed system is reduced, and therefore, it is required to further improve dispersibility of the nano metal oxide by means of, for example, surface modification.
The preparation method of the modified nano metal oxide comprises the following steps: taking nano SiO 2 Or nano Al 2 O 3 Drying, cooling to room temperature, placing in a reaction kettle, adding silane coupling agent solution diluted by absolute ethyl alcohol, dispersing and stirring by ultrasonic,taking out and drying to obtain the surface modified nano metal oxide. The silane coupling agent is preferably one or more of aminopropyl triethoxy silane (APTES), 3-glycidoxy propyl trimethoxy silane, gamma-aminopropyl methyl diethoxy silane and methyl trimethoxy silane.
As a further aspect of the present application, in the functional additive, the antioxidant is a commonly-used commercial product, namely, antioxidant 1010. The antioxidant is hindered phenol, has good compatibility with polyurethane materials, effectively slows down the oxidation of the polyurethane material wiper strip, thereby improving the yellowing resistance, and the higher the antioxidant addition amount is, the better the yellowing resistance is, but excessive antioxidant does not further improve the yellowing resistance, and increases the raw material cost and influences the mechanical properties of the polyurethane material wiper strip, so that the antioxidant addition amount is 0.1-0.5 percent. The ultraviolet absorber is benzotriazole 1130 ultraviolet absorber and hindered amine 292 light stabilizer composition, and the addition amounts are 0.5-2.0% and 0.1-0.5% of the total material mass fraction respectively. The 1130 ultraviolet absorber is hydroxy phenyl benzotriazole ultraviolet absorber, and is used together with hindered amine 292 light stabilizer (Hindered amines Lightstabilizer, HALS). The shared synergistic agent can obviously improve the performance of the polyurethane wiper strip and prevent the polyurethane wiper strip from losing light, cracking, foaming, falling and changing color. The ultraviolet absorber can be directly purchased from the market for products with corresponding specifications, such as Tinuvin1130 and Tinuvin292 of Basf, germany. The silver powder is added in an amount of 0.2-0.5% of the total material mass fraction, and has the main effects of antibacterial, sterilizing and/or durability enhancing activity.
As a further scheme of the application, the preparation method of the polyurethane wiper strip material comprises the following steps:
(A) Preparation of polyurethane prepolymer: weighing the polyol composition according to a proportion, vacuum dehydrating at 100-110 ℃ and negative pressure of minus 0.09-minus 0.1MPa, cooling to below 70 ℃ after the water content is lower than 0.05%, adding isocyanate, heating to 85-95 ℃ for reaction, cooling to below 60 ℃ after the isocyanate (-NCO) content reaches a theoretical endpoint value, and vacuum defoamating to obtain polyurethane prepolymer, and sealing and storing for standby.
(B) Chain extension and vulcanization: heating the polyurethane prepolymer to 80-85 ℃, adding the modified nano metal oxide, the antioxidant, the silver powder and the ultraviolet absorbent, stirring uniformly, adding the metered chain extender, stirring rapidly, pouring into a flat plate mold which is preheated and coated with a release agent after vacuum defoaming, pressing and vulcanizing at 110-120 ℃ for 10-30min when reaching a gel point, demolding, and vulcanizing at 100-120 ℃ for 16-20h to obtain the polyurethane wiper strip material.
As a further scheme of the application, the polyurethane material wiper strip material has the advantages of low hardness, high rebound resilience, mildew resistance, bacteria resistance and yellowing resistance, and simultaneously has excellent wear resistance and wiper working performance, and can be applied to wiper accessories of floor washers.
The technical scheme provided by the embodiment of the application has the beneficial effects that:
the polyurethane material wiper strip compounded by polyether polyol, polyester polyol, alkyl hydroxyl polysiloxane and additives overcomes the defects of non-oil resistance and rapid abrasion of natural rubber materials, solves the problems of ultraviolet resistance, yellowing resistance, weather resistance and poor low-temperature rebound resilience of common single-component polyurethane materials, and comprehensively improves the mechanical properties of the wiper strip material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, embodiments of the present application will be described in further detail below. In the following specific examples and comparative examples, the operations involved were conducted under conventional conditions or conditions recommended by the manufacturer, without specifying the conditions.
The following exemplifies the preparation methods of the polyester polyols-1 to 6 used in examples and comparative examples, comprising the steps of:
1) Vacuumizing the stainless steel reaction kettle, and then charging nitrogen to ensure that no oxygen exists in the reaction system;
2) With continuous nitrogen introduction, phthalic anhydride, diethylene glycol, 1, 6-hexanediol, trimethylolpropane and monobutyl tin oxide as catalysts were added in the order of the amounts of the components indicated in Table 1;
3) Stirring is started and the temperature is raised to the temperature T 1 At the temperature of t 1 The water produced during the reaction was separated off for an hour. Then heating to a temperature T 2 At the temperature of t 2 The acid value is detected after an hour, and the reaction is ended when the acid value is lower than 3mg KOH/g; wherein T is 1 ，t 1 ，T 2 ，t 2 The values of (2) are shown in Table 2.
TABLE 1 polyester polyol 1-6 parts by weight of the components
TABLE 2 preparation conditions of polyester polyols 1 to 6
Preparation conditions Temperature T 1 (℃) Time t 1 (h) Temperature T 2 (℃) Time t 2 (h)
Polyester polyol-1 150 1 170 10
Polyester polyol-2 145 2 175 8
Polyester polyol-3 140 3 180 6
Polyester polyol-4 150 3 175 7
Polyester polyol-5 150 2 170 8
Polyester polyol-6 140 2 180 9
The following exemplifies the preparation methods of polyurethane prepolymers-1 to 9 used in examples and comparative examples, comprising the steps of:
1) According to the formulation given in Table 3, different polyether polyols, polyester polyols, hydroxy polybutadiene (HTPB) and alkyl hydroxy polysiloxane are mixed according to the weight ratio, and vacuum dehydrated for 2 hours under the negative pressure of 100-0.09-0.10 MPa;
2) After the water content is lower than 0.05%, cooling to 70 ℃, adding Hexamethylene Diisocyanate (HDI), and heating to 85 ℃ for reaction for 3 hours;
3) And cooling to 60 ℃ after the content of isocyanate groups (-NCO) reaches a theoretical end point value, and vacuum defoaming for 0.5h to obtain polyurethane prepolymer 1-9, and sealing and storing for later use.
TABLE 3 polyurethane prepolymers-1 to 9
The following illustrates the preparation methods of the modified nano metal oxides used in examples and comparative examples, comprising the steps of:
taking nano SiO 2 Or Al 2 O 3 Drying at 120 ℃, cooling to room temperature, placing in a reaction kettle, adding silane coupling agent solution diluted by absolute ethyl alcohol, performing ultrasonic dispersion stirring for 0.5h, taking out, drying at 60 ℃ in a blast drying oven, and obtaining the surface modified nano SiO 2 Or Al 2 O 3 。
Table 4 shows the types of metal oxides and the types of silane coupling agents for modification used in the respective examples and comparative examples:
TABLE 4 Metal oxides and silane coupling agents for modification used in examples
Example 1
Heating polyurethane prepolymer-1 to 85 ℃, and adding modified nano SiO accounting for 1.0% of the total system 2 -1, 0.1% antioxidant 1010, 0.3% silver powder, 1.0% Tinuvin1130 and 0.1% Tinuvin292 UV absorber for 1hAnd then adding a metered chain extender 1, 4-butanediol (adjusting and controlling the isocyanate index to be 1.05), rapidly stirring for 5min, vacuum defoaming for 2min, pouring into a flat plate die which is preheated and coated with a release agent, pressing and vulcanizing at 110 ℃ for 30min when the gel point is reached, demolding, and vulcanizing in a 100 ℃ oven for 16h to obtain the polyurethane wiper strip material-1.
Example 2
Heating polyurethane prepolymer-2 to 85 ℃, and adding modified nano Al accounting for 0.5% of the total system 2 O 3 2, stirring for 1h, adding a metered chain extender of 1, 4-butanediol (adjusting and controlling the isocyanate index to be 1.03), rapidly stirring for 5min, vacuum defoaming for 2min, pouring into a flat plate mold preheated and coated with a release agent, pressing and vulcanizing at 100 ℃ for 30min when the gel point is reached, demolding, vulcanizing in a baking oven at 100 ℃ for 20h, and obtaining the polyurethane material wiper strip material-2.
Example 3
Heating polyurethane prepolymer-3 to 85 ℃, and adding modified nano Al accounting for 2.0% of the total system 2 O 3 1, stirring for 1h, 0.5% of antioxidant 1010, 0.2% of silver powder, 2.0% of Tinuvin1130 and 0.3% of Tinuvin292 ultraviolet absorbent, then adding a metered chain extender 1, 6-hexanediol (with an isocyanate index of 1.03 adjusted and controlled), rapidly stirring for 5min, vacuum defoaming for 2min, pouring into a flat plate mold which is preheated and coated with a release agent, pressing and vulcanizing at 110 ℃ for 30min when the gel point is reached, demolding, and vulcanizing in a 100 ℃ oven for 18h to obtain the polyurethane material wiper strip material-3.
Example 4
Heating polyurethane prepolymer-4 to 85 ℃, and adding modified nano SiO accounting for 1.5% of the total system 2 2, 0.4% of antioxidant 1010, 0.4% of silver powder, 1.0% of Tinuvin1130 and 0.3% of Tinuvin292 ultraviolet absorbent, stirring for 1h, adding a metered amount of chain extender 1, 6-hexanediol (adjusting and controlling the isocyanate index to be 1.03), rapidly stirring for 5min, vacuum defoaming for 2min, pouring into a flat plate mold which is preheated and coated with a release agentAnd when the gel point is reached, carrying out press vulcanization for 30min at 110 ℃, demolding, and vulcanizing in a 100 ℃ oven for 18h to obtain the polyurethane wiper strip material-4.
Example 5
Heating polyurethane prepolymer-5 to 85 ℃, and adding modified nano Al accounting for 0.8% of the total system 2 O 3 1, stirring for 1h, 0.3% of antioxidant 1010, 0.3% of silver powder, 2.0% of Tinuvin1130 and 0.5% of Tinuvin292 ultraviolet absorbent, then adding a metered chain extender 1, 6-hexanediol (with an isocyanate index of 1.03 adjusted and controlled), rapidly stirring for 5min, vacuum defoaming for 2min, pouring into a flat plate mold which is preheated and coated with a release agent, pressing and vulcanizing at 110 ℃ for 30min when the gel point is reached, demolding, and vulcanizing in a 100 ℃ oven for 20h to obtain the polyurethane wiper strip material-5.
Example 6
Heating polyurethane prepolymer-6 to 85 ℃, and adding modified nano SiO accounting for 0.5% of the total system 2 2, stirring for 1h, adding a metered chain extender of 1, 6-hexanediol (with an isocyanate index of 1.05 adjusted and controlled), rapidly stirring for 5min, vacuum defoaming for 2min, pouring into a flat plate mold which is preheated and coated with a release agent, pressing and vulcanizing at 110 ℃ for 30min when the gel point is reached, demolding, vulcanizing in a baking oven at 100 ℃ for 20h, and obtaining the polyurethane wiper strip material-6.
Comparative example 1
Heating polyurethane prepolymer-7 to 85 ℃, and adding modified nano SiO accounting for 0.5% of the total system 2 1, stirring for 1h, 0.3% of antioxidant 1010, 0.3% of silver powder, 2.0% of Tinuvin1130 and 0.5% of Tinuvin292 ultraviolet absorbent, then adding a metered chain extender 1, 6-hexanediol (with an isocyanate index of 1.05 adjusted and controlled), rapidly stirring for 5min, vacuum defoaming for 2min, pouring into a flat plate mold which is preheated and coated with a release agent, pressing and vulcanizing at 110 ℃ for 30min when the gel point is reached, demolding, and vulcanizing in a 100 ℃ oven for 20h to obtain the polyurethane material wiper strip material-7.
Comparative example 2
Heating polyurethane prepolymer-8 to 85 ℃, and adding modified nano SiO accounting for 0.5% of the total system 2 1, stirring for 1h, 0.3% of antioxidant 1010, 0.3% of silver powder, 2.0% of Tinuvin1130 and 0.5% of Tinuvin292 ultraviolet absorbent, then adding a metered chain extender 1, 6-hexanediol (with an isocyanate index of 1.05 adjusted and controlled), rapidly stirring for 5min, vacuum defoaming for 2min, pouring into a flat plate mold which is preheated and coated with a release agent, pressing and vulcanizing at 110 ℃ for 30min when the gel point is reached, demolding, and vulcanizing in a 100 ℃ oven for 20h to obtain the polyurethane material wiper strip material-8.
Comparative example 3
Heating polyurethane prepolymer-9 to 85 ℃, and adding modified nano SiO accounting for 0.5% of the total system 2 1, stirring for 1h, 0.3% of antioxidant 1010, 0.3% of silver powder, 2.0% of Tinuvin1130 and 0.5% of Tinuvin292 ultraviolet absorbent, then adding a metered chain extender 1, 6-hexanediol (with an isocyanate index of 1.05 adjusted and controlled), rapidly stirring for 5min, vacuum defoaming for 2min, pouring into a flat plate mold which is preheated and coated with a release agent, pressing and vulcanizing at 110 ℃ for 30min when the gel point is reached, demolding, and vulcanizing in a 100 ℃ oven for 20h to obtain the polyurethane material wiper strip material-9.
Comparative example 4
Heating polyurethane prepolymer-1 to 85 ℃, and adding modified nano SiO accounting for 0.5% of the total system 2 Stirring 1h of silver powder with 0.3 percent of silver powder, adding a metered chain extender of 1, 6-hexanediol (adjusting and controlling the isocyanate index to be 1.05), rapidly stirring for 5min, vacuum defoaming for 2min, pouring into a flat plate mold which is preheated and coated with a release agent, pressing and vulcanizing at 110 ℃ for 30min when the gel point is reached, demolding, vulcanizing in a 100 ℃ oven for 20h, and obtaining the polyurethane wiper strip material-10.
The foregoing embodiment numbers of the present application are merely for the purpose of description, and do not represent the advantages or disadvantages of the embodiments.
The foregoing description of the preferred embodiments of the application is not intended to limit the application to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the application are intended to be included within the scope of the application.
The samples obtained in the above examples were left to cure for one week at room temperature and then tested for the properties of the bars under the following test conditions:
hardness: the Shore hardness is tested according to ISO 48-1994 standard, the test instrument is a TIME54420 type Shore hardness tester manufactured by Peking age Peak technology Co., ltd, the test temperature is 25 ℃, the humidity is 46%, and the sample thickness is 6mm;
500% modulus and tensile strength: the preparation of the test sample is carried out according to GB 1039, the test standard is carried out according to ASTM D412-98a (Die D), and the test instrument is a CMT4303 type electronic universal tensile tester manufactured by Meter Industrial systems Co., ltd;
abrasion resistance: according to DIN-53516 standard, the minimum thickness of the sample wafer is 6mm, the test temperature is 23+/-2 ℃, the humidity is 40-50RH, and the test instrument is an NBS abrasion tester;
rebound rate: according to BS 903:part A8:1990 standard test, the test instrument is an 1121 type rubber impact elasticity tester produced by Jiangdu experiment mechanical factory;
degree of yellowing: the samples were observed for change in apparent color after exposure to sunlight for 2 months.
The detailed test results of the polyurethane wiper strip materials prepared in examples 1 to 6 and comparative examples 1 to 4 are shown in Table 5.
TABLE 5 Performance test of different polyurethane materials for wiper strip materials
From the above data, it can be seen that if polyester polyol or alkyl hydroxy polysiloxane or hydroxy terminated polybutadiene or functional additive (comparative examples 1-4) is not added, the hardness, tensile strength, abrasion resistance and anti-yellowing properties of the material are somewhat reduced. The polyurethane wiper strip materials prepared in examples 1-6 all had hardness less than or equal to Shore H A 40, the 500 percent modulus is higher than or equal to 2MPa, the tensile strength is not lower than 11MPa,the resilience of the characteristics is higher than 69%, so that the wiper strip can realize better wiper working effect in practical application; the wear rate is below 85mg/40M, and the excellent wear resistance ensures that the wiper strip material protected by the application can realize longer service time. The wiper strip material prepared in the examples is only slightly yellow after two months of exposure, which indicates that the yellowing resistance of the material is greatly improved.
In summary, the technical scheme provided by the application can realize the optimization of the polyurethane material wiper strip material in the aspects of hardness, wear resistance, rebound resilience, yellowing resistance and the like, so that the polyurethane material wiper strip material has excellent wiper effect and durability in practical application.

Claims (6)

1. The polyurethane wiper strip material is characterized in that the raw materials of the polyurethane wiper strip material comprise: polyol composition, isocyanate, chain extender and modified nano SiO 2 Or modified nano Al 2 O 3 And a functional additive, wherein the polyol composition comprises a polyether polyol, a polyester polyol, an alkyl hydroxy polysiloxane, and a hydroxy terminated polybutadiene; the polyether polyol is one or more of polyoxypropylene-polyoxyethylene dihydric alcohol and polytetrahydrofuran ether glycol with the number average molecular weight of 500-3000 g/mol; the preparation steps of the polyester polyol are as follows: after vacuumizing and introducing nitrogen into a reaction kettle, adding phthalic anhydride, diethylene glycol, 1, 6-hexanediol, trimethylolpropane and monobutyl tin oxide into the reaction kettle, starting stirring, heating to 140-150 ℃, preserving heat, removing water generated in the reaction process, heating to 170-180 ℃, and preserving heat until the acid value of the reaction solution is lower than 3mgKOH/g, wherein the reaction is finished when the phthalic anhydride is calculated according to the weight part ratio: diethylene glycol: 1, 6-hexanediol: trimethylolpropane=51-54:10-25:12-25:10-20; the structural general formula of the alkyl hydroxyl polysiloxane is as follows:
wherein n is an integer between 5 and 20, and a+b is an integer between 4 and 10;
the isocyanate is hexamethylene diisocyanate or isophorone diisocyanate;
the chain extender is 1, 4-butanediol or 1, 6-hexanediol; the functional additive comprises an antioxidant, silver powder and an ultraviolet absorber.
2. The polyurethane wiper strip material as set forth in claim 1, wherein the hydroxyl-terminated polybutadiene has a number average molecular weight of 2000 to 4000g/mol.
3. The polyurethane wiper strip material as set forth in claim 1, wherein said modified nano SiO 2 Or modified nano Al 2 O 3 The addition amount of the catalyst is 0.5-2.0% of the total weight of the material, and the preparation method is as follows: taking nano SiO cooled to room temperature after drying 2 Or nano Al 2 O 3 Placing the mixture into a reaction kettle, adding a silane coupling agent solution diluted by absolute ethyl alcohol, performing ultrasonic dispersion, and drying to obtain the surface modified nano SiO 2 Or nano Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the silane coupling agent is one or more of aminopropyl triethoxysilane, 3-glycidol ether oxygen propyl trimethoxy silane, gamma-aminopropyl methyl diethoxy silane and methyl trimethoxy silane.
4. The polyurethane wiper strip material as set forth in claim 1, wherein the antioxidant is antioxidant 1010, and the addition amount is 0.1-0.5% of the total weight of the material; the addition amount of the silver powder is 0.2-0.5% of the total weight of the material; the ultraviolet absorber is benzotriazole 1130 ultraviolet absorber and hindered amine 292 light stabilizer composition, and the addition amounts are 0.5-2.0% and 0.1-0.5% of the total weight of the material respectively.
5. The method for preparing the polyurethane wiper strip material as set forth in any one of claims 1 to 4, wherein the method comprises the following steps:
(A) Preparation of polyurethane prepolymer: weighing and mixing the components of the polyol composition according to a proportion, vacuum dehydrating at 100-110 ℃ and 0.1-0.09 MPa, cooling to below 70 ℃ after the water content is lower than 0.05%, adding isocyanate, heating to 85-95 ℃ for reaction, cooling to below 60 ℃ after the isocyanate group content reaches a theoretical end point value, and vacuum defoaming to obtain a polyurethane prepolymer, and sealing and storing for later use;
(B) Chain extension and vulcanization: heating the polyurethane prepolymer to 80-85 ℃, adding the modified nano metal oxide, the antioxidant, the silver powder and the ultraviolet absorbent, stirring uniformly, adding the metered chain extender, stirring rapidly, pouring into a flat plate mold which is preheated and coated with a release agent after vacuum defoaming, pressing and vulcanizing at 110-120 ℃ for 10-30min when the gel point is reached, demolding, and vulcanizing at 100-120 ℃ for 16-20h to obtain the polyurethane wiper strip material.
6. Use of a polyurethane wiper strip material according to any one of claims 1 to 4 in a wiper fitting of a floor cleaning machine.
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Citations (5)

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Publication number Priority date Publication date Assignee Title
DE10022276A1 (en) * 2000-05-09 2001-11-15 Basf Ag Composite material, useful for making e.g. automobile interior components, comprises a polyurethane derived from a specified polyester polyol, adhesively bonded to a thermoplastic substrate
CN102174163A (en) * 2011-01-21 2011-09-07 华南理工大学 Side chain functionalized amphiphilic polyurethane and preparation method and application thereof
CN107602817A (en) * 2017-10-26 2018-01-19 株洲时代新材料科技股份有限公司 A kind of high cold-resistant polyurethane shock pad and preparation method thereof
CN113968958A (en) * 2021-11-26 2022-01-25 广东富强科技股份有限公司 Polyurethane and preparation method and application thereof
CN114206968A (en) * 2019-08-05 2022-03-18 路博润先进材料公司 Thermoplastic polyurethanes and process for preparing thermoplastic polyurethanes and components thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
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DE10022276A1 (en) * 2000-05-09 2001-11-15 Basf Ag Composite material, useful for making e.g. automobile interior components, comprises a polyurethane derived from a specified polyester polyol, adhesively bonded to a thermoplastic substrate
CN102174163A (en) * 2011-01-21 2011-09-07 华南理工大学 Side chain functionalized amphiphilic polyurethane and preparation method and application thereof
CN107602817A (en) * 2017-10-26 2018-01-19 株洲时代新材料科技股份有限公司 A kind of high cold-resistant polyurethane shock pad and preparation method thereof
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CN113968958A (en) * 2021-11-26 2022-01-25 广东富强科技股份有限公司 Polyurethane and preparation method and application thereof

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