CN110606927A - High-performance polyurethane damping material and preparation method thereof - Google Patents

Abstract

The invention discloses a high-performance polyurethane damping material and a preparation method thereof. It consists of a prepolymer or semi-prepolymer component (component A) and a chain extender component (component B). The calculation includes: (1) A component macromolecule polyol 100, diisocyanate 10-200; (2) B component macromolecule polyol 0-100, chain extender 5-50, catalyst 0-2; A/B The ratio is 100/5 to 200. The chain extender has the following structural formula: wherein R is alkyl, branched alkyl, cycloalkyl, aryl, aryl with substituents; R1, R2, R3, R4 are H, alkyl, branched alkyl, cycloalkyl, aryl or Substituted aromatic groups. The material does not introduce damping fillers, graft modification or damping structural units, and there is no risk of increasing the viscosity of the material system. And it has excellent comprehensive mechanical properties and improves the damping performance of the material to meet the requirements of the material preparation process and strength in some special vibration-damping working environments.

Description

A kind of high-performance polyurethane damping material and preparation method thereof

technical field

The invention belongs to the technical field of polyurethane, and in particular relates to a polyurethane material with high strength and high loss factor and a preparation method thereof.

Background technique

With the rapid development of modern industry, there are more and more frequencies and places of vibration and noise, and vibration and noise generated by high automation fill every corner of life. Vibration, shock and noise will cause serious harm to social production and social life. On the one hand, severe vibration directly affects the normal operation of instruments and meters, and brings many outstanding problems to electronic devices, instruments, engineering structures and environmental protection. On the other hand, vibration and noise seriously interfere with people's work and life and endanger human health. Therefore, vibration reduction and noise reduction is an important problem that needs to be solved urgently in many fields. The use of damping materials is one of the most effective ways to control vibration and noise.

Polyurethane materials have a certain damping factor. In order to further improve the damping performance of polyurethane materials, methods such as blending and adding damping fillers, grafting modification or introducing damping structural units are usually used to improve the damping factor. For example, in the patent document CN 108034344A, adding hydroxyl Acrylic resins, damping fillers, sound-absorbing fillers, and materials containing diazofluorene structures are added to improve damping performance; in patent document CN105153394A, filler carbon nanotubes and silica are added to improve the heat resistance and damping properties of the material; Patent document CN 107033324A uses a hydroxyl-terminated hyperbranched polyester, pendant chain prepolymer, etc. to improve damping; Patent document CN 104448289A introduces side groups on the main chain of polyether to increase internal friction and improve damping. However, the introduction of damping fillers, graft modification or the introduction of damping structural units can easily lead to an increase in the viscosity of the material system, uneven dispersion of the filler, etc., resulting in a decrease in material strength, an increase in hardness, and uneven damping performance.

SUMMARY OF THE INVENTION

The first technical problem to be solved by the present invention is to provide a high-performance polyurethane damping material, which does not introduce damping fillers, graft modification or damping structural units, and does not have the risk of increasing the viscosity of the material system. And it has excellent comprehensive mechanical properties and improves the damping performance of the material to meet the requirements of the material preparation process and strength in some special vibration-damping working environments.

The second technical problem to be solved by the present invention is to provide a preparation method of the high-performance polyurethane damping material.

In order to solve the first technical problem, the technical solution adopted in the present invention is: a high-performance polyurethane damping material, which is composed of a prepolymer or semi-prepolymer component (component A) and a chain extender component (component B). points) is composed of two parts, including by weight:

(1) Component A

Macropolyol 100

Diisocyanate 10～200

(2) B component

Macromolecular polyol 0～100

Chain extender 5～50

Catalyst 0～2

The A/B ratio is 100/5 to 200.

The macromolecular polyol includes polyester diol, polyether diol, polytetrahydrofuran diol, polycarbonate diol, etc., the molecular weight is 400-8000, and the average functionality is 1.8-3.0, preferably 1.9-2.0 . Among them, polyester diols include the reaction products of small molecular dicarboxylic acids and small molecular diols, and also include products obtained by reacting various lactones with diols, such as caprolactone and ethylene glycol or diethylene glycol ε-polycaprolactone diol (PCL) etc. prepared by the reaction of alcohol etc.

The diisocyanates include aromatic diisocyanates, aliphatic diisocyanates or alicyclic diisocyanates, etc., such as toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), p-phenylene diisocyanate (PPDI), 1, 5-Naphthalene diisocyanate (NDI), 3,3'-dimethyl-4,4'-biphenyl diisocyanate (TODI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) Or 4,4'-dicyclohexylmethane diisocyanate (H ₁₂ MDI) and the like.

The chain extender has the following structural formula: wherein R is an alkyl group, a branched chain alkyl group, a cycloalkyl group, an aryl group, an aryl group containing substituents, and the like. R1, R2, R3, and R4 are H, alkyl, branched-chain alkyl, cycloalkyl, aryl or substituted aryl and the like.

The catalyst is one or more mixtures of tertiary amines, organic bismuth compounds or organic tin compounds. The tertiary amine catalyst is preferably triethylenediamine; the organic bismuth compound is selected from bismuth isooctanoate, bismuth carboxylate or a combination thereof; the organic tin compound is selected from stannous octoate (T-9), dibutyltin dioctoate or dilaurin One or more of dibutyltin acid (T-12) and the like.

The high-performance polyurethane damping material of the present invention can also be added with conventional additives, such as flame retardants, mold release agents, pigments, hydrolysis stabilizers, antioxidants, plasticizers, antistatic agents or reinforcing agents.

In order to solve the second technical problem, the present invention provides a preparation method of the high-performance polyurethane damping material, comprising the following steps:

(1) Preparation of component A: after removing the water from the macromolecular polyol, add a metered amount of isocyanate, react at 70-100 ° C for 1.5-4 hours, vacuum defoaming, and after reaching the theoretical NCO%, cool down and discharge, and seal it for storage ;

(2) Preparation of component B: the macromolecular polyol, chain extender, catalyst and other auxiliary agents are mixed and stirred evenly according to the metering, and the material is discharged and stored in a sealed manner;

(3) Preparation of elastomer: The material is poured by machine or by hand. The temperature of component A is 20-90 °C, and the temperature of component B is 20-70 °C. The two components are fully mixed and injected into the normal temperature or high temperature mold. In the middle, demoulding, aging at 80-120 ℃ for 16-24 hours, and placing at room temperature for 7 days to test the performance.

The properties of the obtained materials are shown in Table 1.

Table 1 Properties of the high-performance polyurethane damping material according to the present invention

Test items Material properties Hardness/Shore A 50～90 Tensile strength/MPa 25～48 Elongation at break/% 350～600 Maximum loss factor (tanδ) ≥0.6

The high-performance polyurethane damping material of the present invention avoids problems such as the increase in viscosity of the material system caused by the use of damping fillers or graft modification or the introduction of damping structural units, the decrease in material strength, the increase in hardness, and the uneven damping performance caused by uneven dispersion of the filler. . It not only has the advantages of ordinary polyurethane elastomers, that is, a large adjustable range of hardness, high strength and high elongation, and good wear resistance, but also has high damping properties that ordinary polyurethane elastomers do not have. It can be used in damping and vibration reduction occasions that require high material mechanical strength and damping performance.

Detailed ways

The present invention will be further described below in conjunction with the examples.

Chain Extender Molecular Formula:

In the embodiment, the type of chain extender is described as follows:

Example Types of chain extenders R R1 R2 R3 R4 Example 1 Chain Extender 1 -(CH₂)₂- H -CH₃ H H Example 2 Chain Extender 1 -(CH₂)₂- H -CH₃ H H Example 3 Chain Extender 2 -C(CH₃)₂- H H H H Example 4 Chain Extender 1 -(CH₂)₂- H -CH₃ H H

Example 1

(1) Preparation of component A: dehydrate 400 g of polycaprolactone diol with a number-average molecular weight of 2000 at 95 to 100 °C and a vacuum of -0.1 MPa for 2 h, add 160 g of MDI, and react at 70 to 80 °C 1.5h, vacuum defoaming, discharging for use.

(2) Preparation of component B: 100g of chain extender 1 was melted at 80°C, and then mixed with 0.4g of catalyst (a solution with a triethyldiamine content of 33% prepared with propylene glycol), and kept the liquid state.

(3) Preparation of elastomer: Keep component A at 75-80 °C, component B at 70-80 °C, and components A/B in a weight ratio of 100/19 are evenly mixed and deaerated, poured into 120 ℃ mold, demoulding for 60min, vulcanization for 20h after 100℃, and testing performance after 7 days at room temperature. The properties of the obtained materials are shown in Table 1.

Example 2

(1) Preparation of component A: dehydrate 400 g of polytetrahydrofuran diol with a number-average molecular weight of 3000 at 95 to 100 °C under a vacuum of -0.1 MPa for 2 h, add 10 g of TDI, and react at 80 to 90 °C for 2 h. Vacuum defoaming, discharging for use.

(2) Preparation of component B: 100 g of chain extender 1 was melted at 80° C., mixed with 0.6 g of catalyst (T12), and kept in a liquid state.

(3) Preparation of elastomers: Keep component A at 80-85 °C, component B at 70-80 °C, and components A/B in a weight ratio of 100/5 are evenly mixed and deaerated, poured in 100 ℃ mold, demoulding for 60min, vulcanization for 20h after 100℃, and testing performance after 7 days at room temperature. The properties of the obtained materials are shown in Table 1.

Example 3

(1) Preparation of component A: dehydrate 400 g of polyethylene adipate diol with a number average molecular weight of 2000 at 95 to 100 °C and a vacuum of -0.1 MPa for 2 h, add 484 g of MDI, and at 70 to 100 °C. The reaction was carried out at 80 °C for 1.5 h, vacuum defoamed, and the material was discharged for use.

(2) Preparation of component B: 200g of polyethylene adipate diol and 145g of chain extender 2 were melted at 80°C, mixed with 0.2g of T-12, and kept in a liquid state.

(3) Preparation of elastomer: Keep component A at 45-55 °C, component B at 45-50 °C, and components A/B in a weight ratio of 100/95.5 are evenly mixed and degassed, and poured into 120 ℃ mold, demoulding for 60min, vulcanization for 20h after 100℃, and testing performance after 7 days at room temperature. The properties of the obtained materials are shown in Table 1.

Example 4

(1) Preparation of component A: 400 g of polytetrahydrofuran diol with a number average molecular weight of 1000 was dehydrated at 95 to 100 °C under a vacuum of -0.1 MPa for 2 h, added with 112 g of TDI, and reacted at 80 to 90 °C for 2 h. Vacuum defoaming, discharging for use.

(2) Preparation of component B: 100 g of chain extender 1 was melted at 80° C., mixed with 0.6 g of catalyst (T12), and kept in a liquid state.

(3) Preparation of elastomers: Keep component A at 80-85 °C, component B at 70-80 °C, and components A/B in a weight ratio of 100/11.7 are evenly mixed and degassed, and poured into 120 ℃ mold, demoulding for 60min, vulcanization for 20h after 100℃, and testing performance after 7 days at room temperature. The properties of the obtained materials are shown in Table 1.

Comparative Example 1

(1) Preparation of component A: dehydrate 400 g of polycaprolactone diol with a number-average molecular weight of 2000 at 95 to 100 °C and a vacuum of -0.1 MPa for 2 h, add 160 g of MDI, and react at 70 to 80 °C 1.5h, vacuum defoaming, discharging for use.

(2) Preparation of component B: 100g of 1,4-butanediol was melted at 60°C, mixed with 0.4g of catalyst (a solution with a triethyldiamine content of 33% prepared by using propylene glycol), and Keep in liquid state.

(3) Preparation of elastomers: Keep component A at 75-80 °C, component B at 40-50 °C, and components A/B in a weight ratio of 100/6.6 are evenly mixed and degassed, then poured in 120 ℃ mold, demoulding for 60min, vulcanization for 20h after 100℃, and testing performance after 7 days at room temperature. The properties of the obtained materials are shown in Table 2.

The properties of the materials obtained in the embodiment of table 2

Experiment number Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Hardness/Shore A 61 52 85 58 87 Tensile strength/MPa 37 25 42 27 43 Elongation at break/% 530 560 440 585 530 Maximum loss factor (tanδ) 0.8 0.7 0.9 0.75 0.4

Claims (10)

1. A high-performance polyurethane damping material comprises a prepolymer or semi-prepolymer component (A component) and a chain extender component (B component), and comprises the following components in parts by weight:

the chain extender is characterized by having the following structural formula:

wherein R is alkyl, branched alkyl, cycloalkyl, aryl or aryl containing substituent; r1, R2, R3 and R4 are H, alkyl, branched alkyl, cycloalkyl, aryl or aryl containing substituent.

2. The high-performance polyurethane damping material as claimed in claim 1, wherein the macropolyol is polyester diol, polyether diol, polytetrahydrofuran diol or polycarbonate diol, the molecular weight is 400-8000, and the average functionality is 1.8-3.0.

3. The high-performance polyurethane damping material according to claim 2, wherein the polyester diol is a reaction product of small molecule dicarboxylic acid and small molecule diol, or a product obtained by reacting various lactones with diol.

4. The high-performance polyurethane damping material of claim 3, wherein the polyester diol is epsilon-polycaprolactone diol (PCL) prepared by reacting caprolactone with ethylene glycol or diethylene glycol.

5. The high performance polyurethane damping material of claim 1, wherein the diisocyanate is an aromatic diisocyanate, an aliphatic diisocyanate or an alicyclic diisocyanate.

6. The high performance polyurethane damping material of claim 5, wherein the diisocyanate is Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), p-phenylene diisocyanate (PPDI), 1, 5-Naphthalene Diisocyanate (NDI), 3 ' -dimethyl-4, 4 ' -biphenyl diisocyanate (TODI), Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), or 4, 4 ' -dicyclohexylmethane diisocyanate (H)₁₂MDI)。

7. The high-performance polyurethane damping material as claimed in claim 1, wherein the catalyst is one or more of tertiary amine, organic bismuth compound or organic tin compound.

8. The high-performance polyurethane damping material as claimed in claim 7, wherein the tertiary amine catalyst is triethylene diamine; the organic bismuth compound refers to bismuth isocaprylate, bismuth carboxylate or a combination thereof, and the organic tin compound is selected from one or more of stannous octoate (T-9), dibutyltin dioctoate or dibutyltin dilaurate (T-12).

9. The high performance polyurethane damping material of claim 1, wherein the high performance polyurethane damping material comprises a flame retardant, a mold release agent, a pigment, a hydrolytic stabilizer, an antioxidant, a plasticizer, an antistatic agent or a reinforcing agent.

10. A method for preparing the high-performance polyurethane damping material of any one of claims 1 to 9, comprising the steps of:

(1) preparation of component A: after dewatering the macromolecular polyol, adding metered isocyanate, reacting for 1.5-4 h at 70-100 ℃, defoaming in vacuum, cooling and discharging after theoretical NCO% is reached, and sealing and storing;

(2) preparation of the component B: stirring the macromolecular polyol, the chain extender, the catalyst and other auxiliaries according to the measurement, uniformly mixing, discharging, sealing and storing;

(3) preparation of elastomer: the material pouring adopts machine pouring or manual pouring, the temperature of the component A is 20-90 ℃, the temperature of the component B is 20-70 ℃, the two components are fully and uniformly mixed, injected into a normal-temperature or high-temperature mold, demoulded and cured for 16-24 hours at the temperature of 80-120 ℃.