阅读说明：本技术 一种无机微球填充ndi型pur高性能复合微孔弹性体及其制备方法 (Inorganic microsphere filled NDI type PUR high-performance composite microporous elastomer and preparation method thereof ) 是由 陈红 于 2021-01-14 设计创作，主要内容包括：本发明公开了一种无机微球填充NDI型PUR高性能复合微孔弹性体及其制备方法。本发明将无机微球、1,5萘二异氰酸酯预聚体、扩链交联剂和催化剂混合均匀,经过一步浇筑法,聚合反应形成所述复合微孔弹性体,其中,所述无机微球的表面包裹有羧基聚苯乙烯或氨基聚苯乙烯。本发明制备得到的弹性体具有良好的硬度、刚度、强度和阻尼性能,可制备成减震结构件用于高速铁路机车、城际轨道机车、汽车等车辆零部件领域,以减少和缓冲高速冲击过程产生的震动。(The invention discloses an inorganic microsphere filled NDI type PUR high-performance composite microporous elastomer and a preparation method thereof. The composite microporous elastomer is prepared by uniformly mixing inorganic microspheres, a 1, 5-naphthalene diisocyanate prepolymer, a chain-extending cross-linking agent and a catalyst, and performing polymerization reaction by a one-step pouring method, wherein the surface of the inorganic microspheres is coated with carboxyl polystyrene or amino polystyrene. The elastomer prepared by the invention has good hardness, rigidity, strength and damping performance, and can be prepared into a damping structural member for the field of vehicle parts such as high-speed railway locomotives, intercity rail locomotives, automobiles and the like so as to reduce and buffer vibration generated in a high-speed impact process.)

1. A preparation method of an inorganic microsphere filled NDI type PUR high-performance composite microporous elastomer is characterized in that inorganic microspheres, a 1, 5 naphthalene diisocyanate prepolymer, a chain extension cross-linking agent and a catalyst are uniformly mixed, and the composite microporous elastomer is formed through a one-step pouring method and a polymerization reaction, wherein the surfaces of the inorganic microspheres are wrapped by carboxyl polystyrene or amino polystyrene.

2. The method for preparing the inorganic microsphere filled NDI type PUR high-performance composite microporous elastomer according to claim 1, which is characterized by comprising the following steps:

(1) uniformly dispersing inorganic microspheres into the 1, 5-naphthalene diisocyanate prepolymer to obtain a liquid mixture with the viscosity controlled at 2000-3000mPa & s;

(2) and (2) uniformly mixing the liquid mixture obtained in the step (1), a catalyst and a chain extension crosslinking agent, pouring into a mold, and curing and molding to obtain the composite microporous elastomer.

3. The method for preparing the NDI-type PUR high-performance composite microporous elastomer filled with the inorganic microspheres according to claim 1 or 2, wherein the inorganic microspheres comprise TiO₂Microspheres, Al₂O₃Microspheres, ZrO₂At least one of microspheres; the particle size of the inorganic microspheres is not more than 10 μm, preferably 100nm-10 μm.

4. The preparation method of the inorganic microsphere filled NDI type PUR high-performance composite microporous elastomer according to claim 1 or 2, wherein the 1, 5-naphthalene diisocyanate prepolymer is prepared by adding a polymerization inhibitor into polyol and 1, 5-naphthalene diisocyanate under the protection of nitrogen, and reacting at 120-140 ℃ for 30-40 min.

5. The method for preparing the inorganic microsphere filled NDI type PUR high performance composite microporous elastomer according to claim 4, wherein the polyol is at least one of polyether diol, polyester diol and polycaprolactone diol, and the molecular weight of the polyol is 1000-2000.

6. The method for preparing the inorganic microsphere filled NDI type PUR high-performance composite microporous elastomer according to claim 1 or 2, wherein the chain-extending crosslinking agent is at least one of ethylene glycol, 1, 4 butanediol, 1, 2 propylene glycol, neopentyl glycol and trimethylolpropane, preferably 1, 4 butanediol and trimethylolpropane; the catalyst is small molecular diamine.

7. The method for preparing the inorganic microsphere-filled NDI-type PUR high-performance composite microcellular elastomer according to claim 1, wherein the composite microcellular elastomer further comprises at least one of an auxiliary agent, an antioxidant, an anti-hydrolysis agent, a light stabilizer and a mold release agent.

8. The method for preparing the inorganic microsphere-filled NDI-type PUR high-performance composite microporous elastomer according to claim 7, wherein the auxiliary agent comprises at least one of carbodiimide, 2, 6-di-tert-butyl-4-methylphenol, triphenyl phosphite and 2-hydroxy-4-methoxybenzophenone, and the addition amount of the auxiliary agent is not more than 0.01% of the mass of the composite microporous elastomer.

9. The inorganic microsphere filled NDI type PUR high performance composite microcellular elastomer prepared by the method according to any one of claims 1 to 8.

10. A shock absorbing structural member comprising the inorganic microsphere-filled NDI type PUR high performance composite microcellular elastomer according to claim 9.

Technical Field

The invention relates to the technical field of polyurethane elastomer damping structures, in particular to an inorganic microsphere filled NDI type PUR high-performance composite microporous elastomer and a preparation method thereof.

Background

The current damping and buffering structural member is generally a PUR microporous elastomer which is formed by pouring MDI or NDI and polyhydric alcohol through a two-step method. The conventional polyurethane microporous elastomer takes water as a chemical foaming agent to form a microporous structure, and the storage stability of the polymer is poor due to the fact that water and NCO react rapidly and violently to form carbamido or further react to form biuret branching; secondly, the formation reaction of the urea groups can hinder the reaction of NCO and a chain extender crosslinking agent, and is not beneficial to the formation of linear long-chain macromolecules with high molecular weight, so that the hardness and rigidity of the conventional PUR microporous elastomer, no matter of MDI type or NDI type, are always the places to be improved of the materials. In order to overcome the technical defects of the traditional PUR elastomer, the invention aims to provide an inorganic microsphere composite NDI type PUR microporous elastomer without water and foaming agent, which is suitable for parts such as shock absorbers, bearings, overload springs and the like of high-speed railway locomotives, intercity rail locomotives, automobiles and the like so as to reduce and buffer the vibration generated in the high-speed impact process.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides an inorganic microsphere filled NDI type PUR high-performance composite microporous elastomer and a preparation method thereof.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

a preparation method of an inorganic microsphere filled NDI type PUR high-performance composite microporous elastomer comprises the steps of uniformly mixing inorganic microspheres, 1, 5 naphthalene diisocyanate prepolymer, a chain extension cross-linking agent and a catalyst, and carrying out polymerization reaction by a one-step pouring method to form the composite microporous elastomer, wherein the surface of the inorganic microspheres is wrapped by carboxyl polystyrene or amino polystyrene.

The inorganic microspheres are used as filling materials, the surfaces of the inorganic microspheres are organized, a layer of carboxyl polystyrene or amino polystyrene is wrapped on the surfaces of the inorganic microspheres to serve as a protective structure of the microspheres, the microspheres are prevented from being cracked, and organic matters wrapped on the surfaces of the microspheres can serve as an intermediate bridge structure of the inorganic microspheres and the elastomer, so that the inorganic microspheres are effectively and tightly uniformly dispersed in the elastomer, and the hardness, the rigidity, the strength and the damping performance of the elastomer are improved. The elastomer prepared by the invention has good hardness, rigidity, strength and damping performance.

Preferably, the preparation method of the inorganic microsphere filled NDI type PUR high-performance composite microporous elastomer specifically comprises the following steps:

(1) uniformly dispersing inorganic microspheres into the 1, 5-naphthalene diisocyanate prepolymer to obtain a liquid mixture with the viscosity controlled at 2000-3000mPa & s;

(2) and (2) uniformly mixing the liquid mixture obtained in the step (1), a catalyst and a chain extension crosslinking agent, pouring into a mold, and curing and molding to obtain the composite microporous elastomer.

In the step (1), the inorganic microspheres can be uniformly dispersed in the 1, 5-naphthalene diisocyanate prepolymer by mechanical stirring, three-dimensional rotation or high-speed dispersion.

The liquid mixture obtained in step (1) needs to be prepared in situ due to high reactivity of residual NCO in 1, 5-naphthalene isocyanic acid, and preferably, in order to prevent water in air or a trace amount of water in polyol from reacting with NCO, the mixture needs to be subjected to water removal, and molecular sieves can be used for water removal.

The mixing method in the step (2) can be mechanical stirring or stirring by adopting a low-pressure pouring type mixer; the mould is not limited to any shape and can be designed according to the structure of parts, the mould needs to be heated in the curing process, and the temperature is controlled to be 60-80 ℃.

Preferably, the inorganic microspheres comprise TiO₂Microspheres, Al₂O₃Microspheres, ZrO₂At least one of the microspheres ensures that the prepared elastomer has good hardness, rigidity, strength and damping performance.

In order to further improve the hardness, rigidity, strength and damping properties of the elastomer, it is preferable that the particle size of the inorganic microspheres is not more than 10 μm, preferably 100nm to 10 μm.

Preferably, the 1, 5-naphthalene diisocyanate prepolymer (NDI prepolymer) is prepared by adding a polymerization inhibitor into polyol and 1, 5-naphthalene diisocyanate under the protection of nitrogen, and reacting at 120-140 ℃ for 30-40 min.

Preferably, the polyol is at least one of polyether diol, polyester diol and polycaprolactone diol, and the molecular weight of the polyol is 1000-2000.

Preferably, the chain-extending crosslinking agent is at least one of ethylene glycol, 1, 4-butanediol, 1, 2-propanediol, neopentyl glycol and trimethylolpropane, preferably 1, 4-butanediol and trimethylolpropane; the catalyst is small molecular diamine.

Preferably, the composite microcellular elastomer further comprises at least one of an auxiliary agent, an antioxidant, an anti-hydrolysis agent, a light stabilizer and a mold release agent.

Preferably, the auxiliary agent comprises at least one of carbodiimide, 2, 6-di-tert-butyl-4-methylphenol, triphenyl phosphite and 2-hydroxy-4-methoxybenzophenone, and the addition amount of the auxiliary agent is not more than 0.01% of the mass of the composite microporous elastomer.

The invention also provides the NDI type PUR high-performance composite microporous elastomer filled with the inorganic microspheres prepared by the method.

The invention also provides a shock-absorbing structural part which comprises the inorganic microsphere filled NDI type PUR high-performance composite microporous elastomer. The shock-absorbing structural part can be used in the field of vehicle parts such as high-speed railway locomotives, intercity rail locomotives, automobiles and the like, can effectively absorb energy generated in the vibration process of devices, and plays a role in shock absorption and buffering.

Compared with the prior art, the invention has the beneficial effects that:

according to the invention, raw material components are preferably selected, the prepared elastomer has good hardness, rigidity, strength and damping performance, and can be prepared into a shock absorption structural part for the fields of vehicle parts such as high-speed railway locomotives, intercity rail locomotives, automobiles and the like.

Drawings

FIG. 1 is a schematic view of the shock absorbing structure of the present invention.

Detailed Description

To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples. It will be understood by those skilled in the art that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

In the examples, the experimental methods used were all conventional methods unless otherwise specified, and the materials, reagents and the like used were commercially available without otherwise specified.

PTMG 1000: polycarbonate diol, molecular weight 1000, japan xylonite corporation;

PCL-220: polycaprolactone diol, molecular weight 2000, japan xylonite.

The damping structure member of examples 1-2 is shown in fig. 1, the material of the damping structure member is an inorganic microsphere filled NDI type PUR high-performance composite microcellular elastomer, the main formula of the elastomer is shown in table 1, and the specific preparation method comprises the following steps:

(1) adding a polymerization inhibitor into polyol and 1, 5-naphthalene diisocyanate under the protection of nitrogen, and reacting at 130 ℃ for 35min to obtain a 1, 5-naphthalene diisocyanate prepolymer; wrapping Al with carboxyl polystyrene₂O₃Uniformly dispersing inorganic microspheres into the 1, 5-naphthalene diisocyanate prepolymer by mechanical stirring to obtain a liquid mixture with the viscosity controlled at 3000mPa & s;

(2) and (2) uniformly stirring and mixing the liquid mixture obtained in the step (1), the small-molecular diamine, the auxiliary agent and the chain extension crosslinking agent, pouring the mixture into a designed mould, and curing and molding the mixture by a one-step pouring method to obtain the composite microporous elastomer, wherein the specific process parameters are shown in table 2.

TABLE 1

TABLE 2

The vibration damping structure member of comparative example 1 was substantially the same in preparation method and composition as example 1, except that Al of this comparative example₂O₃The surface of the inorganic microsphere does not contain carboxyl polystyrene.

The above elastomeric structures were subjected to performance testing and the results are shown in table 3:

TABLE 3

The results show that the shock-absorbing structural part has excellent damping performance, can effectively absorb energy generated in the shock process of the device to play a role in shock absorption and buffering, and is suitable for the field of vehicle parts such as high-speed railway locomotives, intercity rail locomotives, automobiles and the like.

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.