CN113563563A - Low-density fatigue-resistant microporous polyurethane elastic damping pad and preparation method thereof - Google Patents
Low-density fatigue-resistant microporous polyurethane elastic damping pad and preparation method thereof Download PDFInfo
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/48—Polyethers
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
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- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
Abstract
The invention relates to a low-density fatigue-resistant microporous polyurethane elastic damping pad and a preparation method thereof, belonging to the technical field of polyurethane microporous elastomers. The vibration damping pad is obtained by curing and molding the component A and the component B; the component A is composed of PTMEG1000, PTMEG2000, EP330, BDO and H2O, an organic phosphorus flame retardant, a foam stabilizer, a mildew inhibitor, BDMAE and T12 are mixed uniformly to prepare the composite material; the component B is prepared by stirring isocyanate and polytetrahydrofuran ether polyol at the temperature of 80-100 DEG CForming a prepolymer with-NCO value of 12-14 within 4-6 h; the molar ratio of active-H contained in the component A to-NCO groups contained in the component B is 1.00: 0.98-1.00: 1.03. The damping pad is used for a secondary bearing structure of a building foundation, has a good damping effect and excellent fatigue resistance, and also has fireproof and mildew-proof functions.
Description
Technical Field
The invention relates to a low-density fatigue-resistant microporous polyurethane elastic damping pad and a preparation method thereof, belonging to the technical field of polyurethane microporous elastomers.
Background
With the gradual encryption of urban traffic networks and the increasing shortage of urban land, the building is closer to the vibration source which frequently generates vibration, such as subways, railways, expressways, airports and the like, and the problem of vibration and noise pollution to the surrounding environment is increasingly serious. How to ensure the comfort of personnel in buildings such as houses, hospitals, scientific research buildings and the like near the vibration sources, reduce the influence on the operation of precision instruments and equipment, prolong the service life of the buildings and improve the land utilization rate is an urgent problem to be solved.
The foundation is laid with vibration damping pads with good vibration damping effect at the bottom and the side of the foundation, so that the influence of a vibration source on the interior of a building can be effectively reduced. The damping pad is divided into 3 types according to different actual bearing: (1) the damping pad is paved under the main bearing structure column of the ground base surface; (2) the ground surface is secondarily loaded with the damping pad; (3) damping pads for the side walls of the foundation; among them, the sub-bearing vibration damping pad of the ground base surface requires lower density and better fatigue resistance.
In the early period, a small number of buildings aim at earthquake resistance, a rubber shock insulation support layer is paved on a foundation, but rubber materials are easy to generate permanent deformation under a long-term load state, the shock absorption effect is reduced and even lost quickly, and particularly near a long-term frequent vibration environment such as a subway and the like, the service life is usually less than 5 years, even less than 1 year and far shorter than that of the building. In addition, the rubber vibration damping cushion product has an unsatisfactory vibration damping effect on high-frequency vibration generated by the operation of vibration sources such as subways.
The microporous polyurethane elastic damping pad is commonly used in the field of rail transit at present, and is a series of microporous polyurethane elastic damping pads developed by North China science and technology Limited company, after 300 ten thousand times of fatigue tests are carried out under corresponding loads (the temperature is kept at 23 +/-2 ℃ for 24 hours, the loading frequency is 4 +/-1 Hz, and the load cycle is 3 multiplied by 106Second), the performance change meets the requirement of fatigue resistance in TB/T3395.1 annex C, the permanent deformation is less than 10%, and the rigidity change rate is less than 15%. If the microporous polyurethane elastic damping pad is applied to the field of buildings, the buildings are influenced by frequent high-frequency vibration of peripheral vibration sources for a long time, and meanwhile, the foundation damping pad is ensured to be used for 70 years or even hundreds of years in the buildings, so that the damping pad is required to have a good damping effect, and the fatigue resistance of the damping pad product is required to be further greatly improved; meanwhile, the microporous polyurethane elastic damping pad is required to have certain fireproof and mildewproof capabilities.
Disclosure of Invention
In view of the above, the present invention aims to provide a low-density fatigue-resistant microcellular polyurethane elastic damping pad and a preparation method thereof. The invention optimizes the raw material components and the component content in the damping pad, so that the damping pad can be used in the foundation secondary bearing structure of the building with the height of less than 100 m. The damping pad has a good damping effect on high-frequency vibration generated by urban rail transit under the load of 150 kPa-300 kPa, and after 1000 ten thousand uninterrupted loading fatigue tests, each performance change is small, and the fatigue resistance is excellent; meanwhile, the damping pad has fireproof and mildewproof functions, and meets the damping requirement in the service life of the building.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a low-density fatigue-resistant microporous polyurethane elastic vibration damping pad is obtained by curing and molding a component A and a component B, and the density of the vibration damping pad is 450kg/m3～550kg/m3And the performance of the microporous polyurethane elastic damping pad meets the requirements after the microporous polyurethane elastic damping pad is subjected to a 1000-ten-thousand loading fatigue resistance test.
The component A is prepared by uniformly mixing polyether polyol, a chain extender, a foaming agent, an organic phosphorus flame retardant, a foam stabilizer, a catalyst and a mildew preventive; the polyether polyol is polytetrahydrofuran ether glycol (PTMEG1000) with the molecular weight of 1000, polytetrahydrofuran ether glycol (PTMEG2000) with the molecular weight of 2000 and polyoxypropylene triol (EP330) with the molecular weight of 5000; the chain extender is 1, 4-Butanediol (BDO); the foaming agent is H2O; the foam stabilizer is AK7703 available from Jiangsu Maisrd; the catalysts were bis (dimethylaminoethyl) ether (BDMAE) and dibutyltin dilaurate (T12).
The component A comprises the following raw materials in parts by weight based on 100 parts by weight of the total raw materials for preparing the component A:
the component B is a prepolymer with-NCO value of 12-14 formed by stirring and reacting isocyanate and polytetrahydrofuran ether polyol for 4-6 h at 80-100 ℃ in a protective gas atmosphere;
the component B comprises the following raw materials in parts by mass based on 100 parts of the total mass of the raw materials for preparing the component B:
45-55 parts of isocyanate;
45-55 parts of polytetrahydrofuran ether polyol.
The molar ratio of active-H contained in the component A to-NCO group contained in the component B is 1.00: 0.98-1.00: 1.03. Wherein the active-H is active-H and H in polyol-OH2Sum of active-H in O; the component B containing-NCO groupsThe group refers to-NCO remaining after the reaction of isocyanate and polytetrahydrofuran ether polyol, namely-NCO in the prepolymer.
In the component A:
preferably, the organophosphorus flame retardant is more than one of dimethyl methylphosphonate (DMMP), triethyl phosphate, tris (2-chloropropyl) phosphate and tris (2-chloroethyl) phosphate. More preferably, the organophosphorus flame retardant is DMMP.
Preferably, the mildew preventive is a polyurethane mildew preventive with a brand number of KP-M100 produced by Foshan science Puyin company or a polyurethane mildew preventive with a brand number of M8 produced by Guanguan Guansi remote company. More preferably, the mildew preventive is a polyurethane mildew preventive with the brand number of KP-M100 produced by Foshan science Puyin.
Preferably, H accounts for 100 parts of the total mass of the raw materials for preparing the component A2The mass portion of O is 0.34-0.36, and the mass portion of BDMAE is 0.17-0.19.
Preferably, the component A comprises the following raw materials in parts by weight based on 100 parts by weight of the total raw materials for preparing the component A:
the mildew preventive is a polyurethane mildew preventive with a brand number of KP-M100 produced by Foshan science Puyin company;
in the component B:
preferably, the isocyanate is diisocyanate. More preferably, the isocyanate is diphenylmethane diisocyanate (MDI).
Preferably, the polytetrahydrofuran ether polyol is PTMEG 1000.
Preferably, the components and parts by weight of the raw materials for preparing the component B are as follows, based on 100 parts by weight of the total raw materials for preparing the component B:
50-55 parts of MDI;
PTMEG 100045-50 parts.
Preferably, the protective gas is nitrogen or an inert gas.
Preferably, the molar ratio of the active-H contained in the component A to the-NCO group contained in the component B is 1.00: 0.99-1.00: 1.01.
A preparation method of a low-density fatigue-resistant microporous polyurethane elastic vibration-damping pad comprises the following steps: preheating the component A to 30-34 ℃ and preheating the component B to 38-42 ℃, and then pouring the preheated component A and the preheated component B into a mold preheated to 60-70 ℃ for curing and forming to obtain the low-density fatigue-resistant microporous polyurethane elastic damping pad.
Preferably, the curing and forming temperature is 60-70 ℃ and the time is 10-15 min.
Advantageous effects
(1) The microporous polyurethane elastic damping pad meets the requirement of the building industry on the flame retardant property of a paving material after flame retarding and mildew proof modification; the mildew-proof grade can reach the highest grade standard; after 1000 ten thousand cyclic loading fatigue tests, the material still has good fatigue resistance. Specifically, in the microporous polyurethane elastic vibration damping pad, the flame retardant property of the vibration damping pad is effectively improved by selecting the organic phosphorus flame retardant and controlling the using amount of the organic phosphorus flame retardant; meanwhile, in order to weaken the plasticizing effect of the introduction of the organic phosphorus flame retardant on the polyurethane matrix and improve the fatigue resistance of the vibration damping pad, the invention carries out adaptability adjustment on the component A and the component B: the dosage of long-chain flexible molecules PTMEG2000 in the formula is properly reduced, the dosage of short-chain flexible molecules PTMEG1000 is increased, and the plasticizing effect influence brought by DMMP is counteracted by reducing the free activity capability of the flexible chains. Secondly, the content of the chain extender BDO is properly increased to increase the dosage of diisocyanate (equivalent to increase the content of benzene rings in the matrix), increase the content of hard segments and the number of hydrogen bonds in the polyurethane matrix, increase intermolecular force and limit the free motion of a flexible chain.
(2) In the microporous polyurethane elastic damping pad, the-NCO and the H2Foaming reaction between O quantitatively releases CO2Gas, thus can be adjusted by adjusting H2The dosage of O is used for changing the density of the prepared damping pad; the catalyst BDMAE is-NCO and H2Between O andthe catalyst T-12 is a high-efficiency catalyst for gel reaction between-NCO and-OH. The foaming and gel reaction rates must be matched to prepare the microcellular polyurethane vibration-damping pad with proper closed cell rate, proper microcellular size and size distribution and no defect in appearance. If the gel reaction rate is too fast, the problems of decrease in the growth size of micropores, increase in density, increase in rigidity, and the like may occur. If the foaming reaction rate is too fast, CO produced per unit time2Excessive gas causes a decrease in the closed cell ratio, and in the case of a serious case, a problem of sink-like appearance is caused.
(3) In the microporous polyurethane elastic vibration-damping pad, the AK7703 foam stabilizer with good effect of improving the structure of the foam pores of the system is used, so that the closed porosity of the prepared vibration-damping pad can reach more than 88%, and the size distribution of the foam pores is uniform. The quick response speed of the damping pad to high-frequency vibration can be realized by improving the closed porosity, and low dynamic-static stiffness ratio and high rebound rate are obtained, so that an ideal damping effect is achieved.
(4) The density of the invention is 450kg/m3～550kg/m3The microporous polyurethane elastic vibration damping pad has the bearing range of 150 kPa-300 kPa, can be laid on secondary bearing areas of the ground base surface of a building except for the primary bearing structural columns, and is suitable for vibration damping application of the secondary bearing areas of the ground base of multi-storey and high-rise buildings.
(5) The microporous polyurethane elastic vibration damping pad has low loss factor, dynamic and static rigidity ratio and good rebound resilience, has ideal isolation and reduction effects on frequent high-frequency vibration generated by urban rail transit, can effectively improve the comfort level of personnel in a building, reduces the influence of the high-frequency vibration on the operation of precision instruments and equipment in the building, and reduces the damage of the high-frequency vibration on a building matrix.
Detailed Description
The present invention is further illustrated by the following detailed description, wherein the processes are conventional unless otherwise specified, and the starting materials are commercially available from a public source without further specification.
In the following examples:
the mildew preventive is a polyurethane mildew preventive with a brand number of KP-M100 produced by Foshan science Puyin.
The foam stabilizer is prepared from AK7703 of Meiside corporation of Jiangsu.
Example 1
(1) 25 parts of PTMEG2000, 31 parts of PTMEG1000, 25.1 parts of EP330, 11.8 parts of BDO and 0.36 part of H2Mixing O, 5 parts of DMMP, 1.04 parts of foam stabilizer, 0.50 part of mildew inhibitor, 0.18 part of BDMAE and 0.020 part of T-12 uniformly to obtain a component A;
mixing 52 parts of MDI and 48 parts of PTMEG1000, and stirring and reacting for 4 hours at 85 ℃ under the nitrogen protection atmosphere to obtain a component B with an-NCO value of 13.40;
(2) uniformly mixing the component A preheated to 32 ℃ and the component B preheated to 40 ℃ by a two-component polyurethane casting machine according to the molar ratio (mass ratio is 1.00:1.27) of active-H in the component A to-NCO group in the component B, continuously casting the mixture on the lower surface of a continuously running chain plate, then putting the mixture into a laminator preheated to 65 ℃ for curing and forming at the temperature of 65 ℃ for 10min, and obtaining the product after the product is taken out of the laminator, wherein the density of the product is 450kg/m3The microcellular polyurethane elastic damping pad.
Example 2
(1) 28 parts of PTMEG2000, 30 parts of PTMEG1000, 23.5 parts of EP330, 11.5 parts of BDO and 0.30 part of H2Mixing O, 5.0 parts of DMMP, 1.02 parts of foam stabilizer, 0.50 part of mildew inhibitor, 0.16 part of BDMAE and 0.020 part of T-12 uniformly to obtain a component A;
mixing 52 parts of MDI and 48 parts of PTMEG1000, and stirring and reacting for 4 hours at 85 ℃ under the nitrogen protection atmosphere to obtain a component B with an-NCO value of 13.40;
(2) uniformly mixing the component A preheated to 32 ℃ and the component B preheated to 40 ℃ by a two-component polyurethane casting machine according to the molar ratio (mass ratio is 1.00:1.23) of active-H in the component A to-NCO group in the component B of 1.00:1.00, continuously casting the mixture on the lower surface of a continuously running chain plate, then putting the mixture into a laminator preheated to 65 ℃ for curing and forming at the curing and forming temperature of 65 ℃ for 10min, and obtaining the product after the product is taken out of the laminator, wherein the density of the product is 550kg/m3The microcellular polyurethane elastic damping pad.
Comparative example 1
(1) 15 parts of PTMEG1000, 51 parts of PTMEG2000, 24.1 parts of EP330, 8.3 parts of BDO and 0.35 part of H2Mixing O, 1.059 parts of foam stabilizer, 0.17 part of BDMAE and 0.021 part of T-12 uniformly to obtain a component A;
mixing 50 parts of MDI, 30 parts of PTMEG1000 and 20 parts of PTMEG2000, and stirring and reacting for 4 hours at 85 ℃ under the nitrogen protection atmosphere to obtain a component B with the-NCO value of 13.39;
(2) according to the mol ratio (mass ratio of 1.00:1.00) of active-H in the component A to-NCO group in the component B, uniformly mixing the component A preheated to 35 ℃ and the component B preheated to 45 ℃ by a two-component polyurethane casting machine, and then casting the mixture into a lockable mould preheated to 65 ℃, wherein the volume of an inner cavity is 868cm3The mould is filled with the mixture with the total mass of 390.5g, the mould filled with the mixture is placed at 65 ℃ for solidification for 10min, the mould is filled with the mixture after expansion molding, and the mixture is molded into the mould with the density of 450kg/m3The microcellular polyurethane elastic damping pad.
Comparative example 2
(1) 15 parts of PTMEG1000, 47.5 parts of PTMEG2000, 22.1 parts of EP330, 8.3 parts of BDO and 0.35 part of H2O, 5.0 parts of DMMP, 1.059 parts of foam stabilizer, 0.50 part of mildew inhibitor, 0.17 part of BDMAE and 0.021 part of T-12 are uniformly mixed to obtain a component A;
mixing 50 parts of MDI, 30 parts of PTMEG1000 and 20 parts of PTMEG2000, and stirring and reacting for 4 hours at 85 ℃ under the nitrogen protection atmosphere to obtain a component B with the-NCO value of 13.39;
(2) according to the mol ratio (the mass ratio is 1.00:0.99) of active-H in the component A and-NCO group in the component B, the component A preheated to 35 ℃ and the component B preheated to 45 ℃ are uniformly mixed by a two-component polyurethane casting machine and then are poured into a lockable mould preheated to 65 ℃, and the volume of an inner cavity is 868cm3The mould is filled with the mixture with the total mass of 390.5g, the mould filled with the mixture is placed at 65 ℃ for solidification for 10min, the mould is filled with the mixture after expansion molding, and the mixture is molded into the mould with the density of 450kg/m3The polyurethane microporous elastic damping pad.
Comparative example 3
(1) 15 parts of PTMEG1000, 51 parts of PTMEG2000, 24 parts of EP330, 8.5 parts of BDO and 0.30 part of H2Mixing O, 1.02 parts of AK7703, 0.16 parts of BDMAE and 0.020 parts of T-12 uniformly to obtain a component A;
mixing 50 parts of MDI, 30 parts of PTMEG1000 and 20 parts of PTMEG2000, and stirring and reacting for 4 hours at 85 ℃ under the nitrogen protection atmosphere to obtain a component B with the-NCO value of 13.39;
(2) according to the mol ratio (mass ratio of 1.00:1.00) of active-H in the component A to-NCO group in the component B, uniformly mixing the component A preheated to 35 ℃ and the component B preheated to 45 ℃ by a two-component polyurethane casting machine, and then casting the mixture into a lockable mould preheated to 65 ℃, wherein the volume of an inner cavity is 868cm3The mould is filled with the mixture with the total mass of 477.4g, the mould filled with the mixture is placed at 65 ℃ for solidification for 10min, the mould is filled with the mixture after expansion molding, and the mixture is molded into the mould with the density of 550kg/m3The microcellular polyurethane elastic damping pad.
Various performance tests are respectively carried out on the microporous polyurethane elastic damping pad prepared in the embodiment and the comparative example according to corresponding standards, and the test results are detailed in table 1; wherein, the density test reference standard GB/T1033.1-2008, the static load limit is a theoretical calculated value, the loss factor test reference standard GB/T18258-2000, the tensile strength and elongation at break test reference standard GB/T1040.3-2006, the static rigidity test reference standard TB/T3395.1 (23 +/-2 ℃ heat preservation for 24h, load 1 kN-35 kN), the dynamic and static rigidity ratio test reference standard TB/T3395.1, the rebound rate test reference standard GB/T1681-2009, the compression permanent deformation rate test reference standard GB/T10653 (70 ℃, 22h, 30% compression), the fatigue test reference standard TB/T3395.1 annex C (23 +/-2 ℃ heat preservation for 24h, the cyclic load is 20-80 kN, the loading frequency is 4 +/-1 Hz), the closed cell rate test reference standard GB/T10799-2008, the heat conductivity test refers to GB/T29288-.
TABLE 1
The test results in table 1 show that the microporous polyurethane elastic damping pad prepared in examples 1-2 meets the requirements of various performance indexes, has excellent fatigue resistance, and can meet the use requirements of the damping pad of the secondary bearing structure of the building foundation.
In summary, the invention includes but is not limited to the above embodiments, and any equivalent replacement or local modification made under the spirit and principle of the invention should be considered as being within the protection scope of the invention.
Claims (10)
1. The utility model provides a low density is able to bear or endure tired micropore polyurethane elastic damping pad which characterized in that: the damping pad is obtained by curing and molding the component A and the component B, and the density of the damping pad is 450kg/m3～550kg/m3The microporous polyurethane elastic damping pad;
the component A is composed of PTMEG1000, PTMEG2000, EP330, BDO, H2O, an organic phosphorus flame retardant, a foam stabilizer, a mildew inhibitor, BDMAE and T12 are mixed uniformly to prepare the composite material; the foam stabilizer is AK7703 available from Jiangsu Maisrd;
the component A comprises the following raw materials in parts by weight based on 100 parts by weight of the total raw materials for preparing the component A:
the component B is a prepolymer with-NCO value of 12-14 formed by stirring and reacting isocyanate and polytetrahydrofuran ether polyol for 4-6 h at 80-100 ℃ in a protective gas atmosphere;
the component B comprises the following raw materials in parts by mass based on 100 parts of the total mass of the raw materials for preparing the component B:
45-55 parts of isocyanate;
45-55 parts of polytetrahydrofuran ether polyol;
the molar ratio of active-H contained in the component A to-NCO groups contained in the component B is 1.00: 0.98-1.00: 1.03.
2. A low density fatigue resistant microcellular polyurethane elastomeric vibration damping pad as defined in claim 1, wherein: in the component A: the organic phosphorus flame retardant is more than one of DMMP, triethyl phosphate, tris (2-chloropropyl) phosphate and tris (2-chloroethyl) phosphate; the mildew preventive is a polyurethane mildew preventive with a brand number of KP-M100 produced by Foshan science Punjin company or a polyurethane mildew preventive with a brand number of M8 produced by Guanguan Guansi company;
in the component B: the isocyanate is diisocyanate; the polytetrahydrofuran ether polyol is PTMEG 1000;
the protective gas is nitrogen or inert gas.
3. A low density fatigue resistant microcellular polyurethane elastomeric vibration damping pad as defined in claim 1, wherein: the flame retardant in the component A is DMMP, and the mildew preventive is a polyurethane mildew preventive with a brand number of KP-M100, which is produced by Foshan science Puyin company; the isocyanate in the component B is MDI.
4. A low density fatigue resistant microcellular polyurethane elastomeric vibration damping pad as defined in claim 1, wherein: based on 100 parts of the total mass of the raw materials for preparing the component A, H20.34-0.36 part of O and 0.17-0.19 part of BDMAE.
5. A low density fatigue resistant microcellular polyurethane elastomeric vibration damping pad as defined in claim 1, wherein: the component A comprises the following raw materials in parts by weight based on 100 parts by weight of the total raw materials for preparing the component A:
the mildew preventive is a polyurethane mildew preventive with a brand number of KP-M100 produced by Foshan science Puyin.
6. A low density fatigue resistant microcellular polyurethane elastomeric vibration damping pad as defined in claim 1, wherein: the component B comprises the following raw materials in parts by mass based on 100 parts of the total mass of the raw materials for preparing the component B:
50-55 parts of MDI;
PTMEG 100045-50 parts.
7. A low density fatigue resistant microcellular polyurethane elastomeric vibration damping pad as defined in claim 1, wherein: the molar ratio of active-H contained in the component A to-NCO group contained in the component B is 1.00: 0.99-1.00: 1.01.
8. A low density fatigue resistant microcellular polyurethane elastomeric vibration damping pad as defined in claim 1, wherein: the component A comprises the following raw materials in parts by weight based on 100 parts by weight of the total raw materials for preparing the component A:
the mildew preventive is a polyurethane mildew preventive with a brand number of KP-M100 produced by Foshan science Puyin company;
the component B comprises the following raw materials in parts by mass based on 100 parts of the total mass of the raw materials for preparing the component B:
PTMEG 100045-50 shares;
50-55 parts of MDI;
the molar ratio of active-H contained in the component A to-NCO group contained in the component B is 1.00: 0.99-1.00: 1.01.
9. A method of making a low density fatigue resistant microcellular polyurethane elastomeric vibration pads as defined in any one of claims 1 to 8, wherein: the method comprises the following steps: preheating the component A to 30-34 ℃ and preheating the component B to 38-42 ℃, and then pouring the preheated component A and the preheated component B into a mold preheated to 60-70 ℃ for curing and forming to obtain the low-density fatigue-resistant microporous polyurethane elastic damping pad.
10. A method of making a low density fatigue resistant microcellular polyurethane elastomeric vibration damping pad as defined in claim 9, wherein: the curing and forming temperature is 60-70 ℃ and the time is 10-15 min.
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