BE1031371B1 - FLAME-RETARDANT AND DROPLETS/PARTICLES-FREE POLYURETHANE ANTI-VIBRATION AND SOUND-ABSORBING PAD AND PREPARATION METHOD - Google Patents

Abstract

The present invention relates to a flame-retardant and flame-droplet/particle-free polyurethane anti-vibration and sound-absorbing pad and a preparation method therefor, which belong to the technical field of microporous polyurethane. The pad is formed by solidifying component A and component B; component A is prepared by mixing PTMEG1000, PTMEG2000, EP330, BDO, H2O, foam stabilizer, BDMAE, T12, antifungal agent and flame retardant; component B is a prepolymer formed by stirring and reacting diisocyanate and polytetrahydrofuran ether polyol at 80 to 100°C for 4 to 6 hours.

Description

1 BE2023/5638

ANTI-VIBRATION AND SOUND-ABSORBING PAD IN

FLAME RETARDANT AND FLAME-FREE POLYURETHANE

IGNITED DROPLETS/PARTICLES AND METHOD

OF PREPARATION

FIELD OF THE INVENTION

[0001]The present invention relates to a flame retardant and droplet/particle-free polyurethane anti-vibration and sound-absorbing pad and a preparation method therefor, which belongs to the technical field of microporous polyurethane.

STATE OF THE ART

[0002]Sound insulation of slabs is one of the most important guarantees for the acoustic environment of housing. Poor sound insulation of slabs is an unsolved problem in the residential industry of our country. Occupants often hear various noises from neighbors on the upper and lower floors, such as the sounds of falling objects, footsteps and moving furniture, which can not only harm the harmony between neighbors, but also become a social problem.

[0003]On the reinforced concrete slab, laying a sound insulation layer made of flexible polymer material (called "floating floor"), followed by a layer of cement floor, can significantly reduce the transmission of noise by solids. The conventional anti-vibration and sound-absorbing materials used for floating floors are mainly rubber, cross-linked polyethylene and polystyrene, however, these materials have poor performance in terms of sound insulation, service life and fire resistance. In addition, these materials must be laid thicker to meet the design requirements for sound insulation, which results in a reduction in the actual usable height between floors and an inefficient use of space.

[0004]The anti-vibration and sound-absorbing polyurethane pads have

2 BE2023/5638 excellent vibration damping and sound insulation properties as well as long service life, being an ideal sound insulation material for floating floors. However, polyurethane elastomers are flammable materials, and the combustion process often produces flaming droplets, which is a serious fire hazard. Although polyurethane elastomers modified by conventional flame retardant can also achieve flame retardancy level B1 (non-flammable) or higher, this will result in a significant decline in its vibration damping, sound insulation and service life performance.

CONTENT OF THE INVENTION

[0005]In order to address the drawbacks of the prior art mentioned above, the present invention aims to provide a flame-retardant polyurethane anti-vibration and sound-absorbing pad without flaming droplets/particles and its preparation method.

[0006]For this, the present invention proposes the following technical solution:

[0007]A flame retardant and flame droplet/particle-free polyurethane anti-vibration and sound-absorbing pad, characterized in that said anti-vibration pad is a microporous polyurethane anti-vibration pad, which is formed by solidifying component A and component B and has a density of 200 to 260 kg/M3, an oxygen index of 26 or more, a tensile strength of 1 MPa or more, and an improvement in the impact sound pressure level of 30 dB or more;

[0008] Said component A is prepared by uniformly mixing the polyether polyol, the chain extender, the foaming agent, the foam stabilizer, the catalyst, the flame retardant and the antifungal agent; said polyether polyol comprises polytetrahydrofuran ether glycol of molecular weight 1000 (PTMEG1000), polytetrahydrofuran VTether glycol of molecular weight 2000 (PTMEG2000) and polyoxypropylene triol (EP330) of molecular weight 5000; said agent

3 BE2023/5638 chain extender is 1,4-butanediol (BDO); said foaming agent is H2O; said foam stabilizer is AK8804 foam stabilizer produced by Jiangsu Maysta Company; said catalyst comprises bis(dimethylaminoethyl) ether (BDMAE) and dibutyltin dilaurate (T12); said flame retardant is expandable graphite (EG) and ammonium polyphosphate (APP);

[0009]based on a total mass of 100 ingredient units for the preparation of said component A, the various ingredients and their mass units are as follows:

PTMEG1000 10 to 20 units;

PTMEG2000 25 to 35 units;

EP330 30 to 40 units;

BDO 6 to 10 units;

H20 0.40 to 0.50 units;

AK8804 0.70 to 1.30 units;

Antifungal agent 0.4 to 0.8 units;

BDMAE 0.16 to 0.21 units;

T-12 0.016 to 0.021 units;

EG 10 to 20 units;

APP 4 to 10 units;

[0010]said component B is a prepolymer formed by stirring and reacting diisocyanate and polytetrahydrofuran ether polyol at 80 to 100°C for 4 to 6 hours, having an -NCO value of 12 to 14;

[0011]based on a total mass of 100 ingredient units for the preparation of said component B, the various ingredients and their mass units are as follows:

Diisocyanate 45 to 55 units;

Ether polyol of 45 to 55 units; polytetrahydrofuran

[0012]the molar ratio between active -H contained in said component A and the -NCO group contained in component B is from 1.00:0.98 to 1.03, wherein said active -H is the sum of the active -H contained in the polyol -OH and the -

4 BE2023/5638

Active H contained in H2O; the -NCO group contained in component B is the -NCO remaining after the reaction of the isocyanate with the polytetrahydrofuran ether polyol, i.e. the -NCO in the prepolymer.

[0013]In component A:

[0014]Preferably, in component A, said antifungal agent is a polyurethane antifungal agent KP-M100 produced by Foshan Company.

KEPUYIN or a polyurethane antifungal agent M8 produced by the company

Dongguan Guangshiyuan.

[0015]Preferably, based on a total mass of 100 ingredient units for the preparation of said component A, the different ingredients and their mass units are as follows:

PTMEG1000 15 to 18 units;

PTMEG2000 25 to 28 units;

EP330 32 to 35 units;

BDO 8 to 10 units;

H20 0.4 to 0.45 units;

AK8804 0.8 to 1.2 units;

KP-M100 0.4 to 0.6 units;

BDMAE 0.17 to 0.19 units;

T-12 0.018 to 0.020 units;

EG 10 to 14 units;

APP 4 to 8 units.

[0016]Preferably, said EG has a particle size of 100 to 200 meshes and an expansion rate of 250 to 300 mL/g.

[0017]Preferably, said APP has a particle size of 1,500 to 2,000 mesh.

[0018]Preferably, the mass ratio between said EG and said APP is from 1:0.35 to 0.45. More preferably, the mass ratio between said EG and said

APP is 1:0.4.

[0019]In component B:

[0020]Preferably, said disocyanate is diphenylmethane disocyanate (MDI); said polytetrahydrofuran ether polyol is

3 BE2023/5638

PTMEG 1000.

[0021]Preferably, based on a total mass of 100 ingredient units for the preparation of said component B, the different ingredients and their mass units are as follows:

PTMEG1000 45 to 50 units;

MDI 50 to 55 units.

[0022]Preferably, the molar ratio between the active -H contained in said component A and the -NCO group contained in component B is from 1.00:0.99 to 1.01.

[0023]The present invention further provides a method for preparing a flame retardant polyurethane anti-vibration and sound-absorbing pad without flaming droplets/particles according to the invention, said method comprising the following steps: first preheating component A to the temperature of 30 to 34°C and component B to 38 to 42°C, then pouring the preheated component A and the preheated component B into a mold preheated to 60 to 70°C to perform solidification forming, in order to obtain a flame retardant polyurethane anti-vibration and sound-absorbing pad without flaming droplets/particles.

[0024]Preferably, the solidification forming temperature is 60 to 70°C and the duration is 10 to 15 min.

[0025]The beneficial effects

[0026](1) The flame retardant and droplet/particle-free polyurethane anti-vibration and sound-absorbing pad according to the present invention, modified by adding APP and EG flame retardant, its oxygen index can reach 26 or more, its flame retardancy level reaches B2 level, and combustion will not produce droplets/particles.

[0027](2) Adding EG alone can solve the problem of flaming droplets, however, there is a large gap between the expanded carbon layer, the bonding strength with the substrate is weak, it is easy for the flame to fall off with the carbon slag (hereinafter referred to as the slag falling off phenomenon), and it does not significantly improve the oxygen index; adding APP alone can improve the oxygen index, but for

6 BE2023/5638 solve the problem of flaming droplets, it is necessary to add a large amount, which will lead to an increase in rigidity and viscosity and a decrease in technological performance; according to the present invention, the combination of EG and APP can play an effective synergistic role, the thermal decomposition products of APP can fill the voids of the expanded carbon layer and increase its density, thereby insulating heat and air well and greatly improving the flame retardant performance, that is, the total amount of flame retardant added is reduced under the premise of a comparable oxygen index.

[0028](3) Advantageously, too small a particle size of the EG results in poor flame retardant effect, too large a particle size may cause poor dispersion in the substrate and affect the closed porosity of the microporous polyurethane elastomer, the optimum particle size of the EG is thus 100 to 200 meshes. Too low an expansion rate of the EG results in poor flame retardant effect, and too high an expansion rate results in weaker bonding with the substrate and causing the phenomenon of slag falling, the optimum expansion rate of the EG is thus 250 to 300 mL/g. Too large a particle size of the APP may cause poor dispersion in the substrate and affect the closed porosity of the microporous polyurethane elastomer, the optimum particle size of the APP is thus 1500 to 2000 meshes. When the amount of APP is relatively small, the thermal decomposition products cannot effectively fill the voids of the expanded carbon layer, resulting in low strength of the carbon layer, weak bonding between the carbon layer and the substrate, and the phenomenon of slag falling; when the amount of APP is relatively large, the rigidity increases; the mass ratio of EG and APP is 1:0.35 to 0.45, which can achieve better synergy between the two, in this case, the oxygen index is high, the total amount of flame retardant without flaming droplets/particles is the smallest, and no impact is produced on other mechanical and sound insulation properties, thus ensuring the effect of using the anti-vibration pad.

[0029](4) When the total amount of flame retardant continues

7 BE2023/5638 to increase, although it can further increase the flame retardant performance, it will affect the sound insulation and other properties as well as the normal use of the anti-vibration pad.

[0030](5) The anti-vibration and sound-absorbing pad according to the present invention has a service life of more than 50 years, allowing it to live with the building; for the 6 mm thick polyurethane anti-vibration and sound-absorbing pad, the weighted standardized impact noise level is only 57 dB, which meets the requirements described in the Code for the Design of Sound Insulation of Civil Buildings (GB/T 50118) (<75 dB for subfloors of bedrooms and living rooms in ordinary residential buildings, and <65 dB for residential buildings with high requirements).

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0031]The present invention is described in detail below in connection with the embodiments. Unless expressly indicated, the methods described are conventional; unless expressly indicated, the ingredients described are available from open commercial sources.

[0032]According to the following embodiments:

[0033]The antifungal agent used is a polyurethane antifungal agent.

KP-M100 produced by Foshan KEPUYIN company.

[0034]The foam stabilizer used is AK8804 foam stabilizer produced by Jiangsu Maysta Company.

[0035]Embodiment 1:

[0036](1) Thoroughly mix 15 units of PTMEG2000, 25 units of PTMEG 1000, 32 units of EP330, 8 units of BDO, 0.4 units of H2O, 0.8 units of foam stabilizer, 0.4 units of antifungal agent, 0.18 units of BDMAE, 0.020 units of T-12, 13 units of EG and 5.2 units of APP, to obtain a component A; mix 50 units of MDI and 50 units of PTMEG1000, and then, under a nitrogen atmosphere, carry out stirring and reaction at 85°C for 4 h, to obtain a component B having a -NCO value of 12.57%;

[0037](2) According to the molar ratio of 1.00:1.00 between the active -H contained in

8 BE2023/5638 component A and the -NCO group contained in component B, thoroughly mix component A preheated to 32°C and component B preheated to 40°C by means of a two-component polyurethane casting machine, and pour the resulting mixture into a mold preheated to 60 to 70°C to perform solidification forming (different densities of polyurethane anti-vibration and sound-absorbing pads can be obtained by controlling the poured volume), so as to obtain a flame-retardant polyurethane anti-vibration and sound-absorbing pad without flaming droplets/particles.

[0038]Control example 1:

[0039](1) Thoroughly mix 17 units of PTMEG2000, 25 units of PTMEG1000, 30 units of EP330, 8 units of BDO, 0.6 units of H2O, 0.8 units of foam stabilizer, 0.4 units of antifungal agent, 0.18 units of BDMAE, 0.020 units of T-12, 15 units of EG and 3 units of APP, to obtain a component A; mix 50 units of MDI and 50 units of PTMEG1000, and then, under a nitrogen atmosphere, carry out stirring and reaction at 85°C for 4 h, to obtain a component B having a -NCO value of 12.57%;

[0040](2) According to the molar ratio of 1.00:1.00 between the active -H contained in component A and the -NCO group contained in component B, thoroughly mix component A preheated to 32°C and component B preheated to 40°C by means of a two-component polyurethane casting machine, and pour the obtained mixture into a mold preheated to 60 to 70°C to perform solidification forming, so as to obtain a polyurethane anti-vibration and sound-absorbing pad without flaming droplets/particles.

[0041]Control example 2:

[0042](1) Thoroughly mix 20 units of PTMEG2000, 30 units of PTMEG 1000, 32 units of EP330, 8 units of BDO, 0.4 units of H2O, 0.8 units of foam stabilizer, 0.6 units of antifungal agent, 0.18 units of BDMAE, 0.020 units of T-12, 5 units of EG and 3 units of APP, to obtain a component A; mix 50 units of MDI and 50 units of PTMEG1000, and then, under a nitrogen atmosphere, carry out stirring and reaction at 85°C for 4 h, to obtain a component B having a -NCO value of 12.57;

[0043](2) According to the molar ratio of 1.00:1.00 between the active -H contained in

9 BE2023/5638 component A and the -NCO group contained in component B, thoroughly mix component A preheated to 32°C and component B preheated to 40°C by means of a two-component polyurethane casting machine, and pour the resulting mixture into a mold preheated to 60 to 70°C to perform solidification forming, in order to obtain a polyurethane anti-vibration and sound-absorbing pad with flaming droplets/particles.

[0044]Control example 3:

[0045](1) Thoroughly mix 20 units of PTMEG2000, 35 units of PTMEG1000, 35 units of EP330, 8 units of BDO, 0.4 units of H2O, 0.8 units of foam stabilizer, 0.6 units of antifungal agent, 0.18 units of BDMAE and 0.020 units of T-12, to obtain a component A; mix 50 units of MDI and 50 units of PTMEG1000, and then, under a nitrogen atmosphere, carry out stirring and reaction at 85°C for 4 h, to obtain a component B having an -NCO value of 12.57;

[0046](2) According to the molar ratio of 1.00:1.00 between the active -H contained in component A and the -NCO group contained in component B, thoroughly mix component A preheated to 32°C and component B preheated to 40°C by means of a two-component polyurethane casting machine, and pour the obtained mixture into a mold preheated to 60 to 70°C to perform solidification forming, so as to obtain a polyurethane anti-vibration and sound-absorbing pad with flaming droplets/particles.

[0047]Control example 4:

[0048](1) Thoroughly mix 17 units of PTMEG2000, 25 units of PTMEG1000, 30.2 units of EP330, 8 units of BDO, 0.4 units of H2O, 0.8 units of foam stabilizer, 0.4 units of antifungal agent, 0.18 units of BDMAE, 0.020 units of T-12 and 18 units of EG, to obtain a component A; mix 50 units of MDI and 50 units of PTMEG1000, and then, under a nitrogen atmosphere, carry out stirring and reaction at 85°C for 4 h, to obtain a component B having an -NCO value of 12.57;

[0049](2) According to the molar ratio of 1.00:1.00 between the active -H contained in component A and the -NCO group contained in component B, mix well the component A preheated to 32°C and the component B preheated to 40°C at

10 BE2023/5638 using a two-component polyurethane casting machine, and pouring the resulting mixture into a mold preheated to 60 to 70°C to perform solidification forming, in order to obtain a polyurethane anti-vibration and sound-absorbing pad with flaming droplets/particles.

[0050]Control example 5:

[0051](1) Thoroughly mix 20 units of PTMEG2000, 25 units of PTMEG1000, 35 units of EP330, 8 units of BDO, 0.6 units of H2O, 0.8 units of foam stabilizer, 0.4 units of antifungal agent, 0.18 units of BDMAE, 0.020 units of T-12 and 10 units of APP, to obtain a component A; mix 50 units of MDI and 50 units of PTMEG1000, and then, under a nitrogen atmosphere, carry out stirring and reaction at 85°C for 4 h, to obtain a component B having an -NCO value of 12.57;

[0052](2) According to the molar ratio of 1.00:1.00 between the active -H contained in component A and the -NCO group contained in component B, thoroughly mix component A preheated to 32°C and component B preheated to 40°C by means of a two-component polyurethane casting machine, and pour the obtained mixture into a mold preheated to 60 to 70°C to perform solidification forming, so as to obtain a polyurethane anti-vibration and sound-absorbing pad with an oxygen index of more than 26 and with flaming droplets/particles.

[0053]In accordance with the relevant standards, various performance tests are carried out on the polyurethane anti-vibration and sound-absorbing pads prepared according to the embodiments and the control examples; in particular, GB/T 2406 applies to the oxygen index, the method described in GB/T 2408-2008 applies to the flaming droplet test, GB/T 10654 applies to the tensile strength test and the elongation at break test, GB/T 10653 applies to the permanent compression deformation test (at 70°C, 22 h and 30% compression), and GB/T 10654 applies to the test of the compressive strength of the polyurethane anti-vibration and sound-absorbing pads prepared according to the embodiments and the control examples.

GB/T 19889.8-2006 on the impact sound pressure level improvement test.

[0054]The performance test results for the embodiments and control examples are detailed in Table 1.

11 BE2023/5638

[0055]Table 1

Example Example

Method of | Example Example of Example of e e realization | of of of control control 1 control 1 | control 2 3 control 4 5

If there are droplets

No No inflamed

Tensile strength (MPa) 1.0 1.3 1.1 0.7

Elongation at break (%) 220 160 260 230 190 180

Permanent deformation in | 3.8 5.3 3.4 3.6 46 48 compression (%)

Impact acoustic pressure level improvement 32 29 32 33 28 27 (dB)

[0056] According to the test results in Table 1, the polyurethane anti-vibration and sound-absorbing pad prepared according to Embodiment 1 has the excellent flame retardant and mechanical properties and good sound insulation effect, which can meet the requirements of using anti-vibration and sound-absorbing pads for floating floors in buildings.

[0057]In summary, the invention includes but is not limited to the above embodiments. The invention extends to any equivalent substitution or partial improvement, which is made in its spirit and in its principles.

Claims (10)

12 BE2023/5638 CLAIMS 1) A flame retardant and droplet/particle-free polyurethane anti-vibration and sound-absorbing pad, characterized in that, said anti-vibration pad is a microporous polyurethane anti-vibration pad, which is formed by solidifying a component A and a component B and has a density of 200 to 260 kg/m3, an oxygen index of 26 or more, a tensile strength of 1 MPa or more, and an improvement in the impact sound pressure level of 30 dB or more; said component A is prepared by uniformly mixing PTMEG1000, PTMEG2000, EP330, BDO, H:0, the foam stabilizer, BDMAE, T12, the antifungal agent and the flame retardant; said foam stabilizer is a foam stabilizer AK8804 produced by Jiangsu Maysta Company; the flame retardant is EG and APP; based on a total mass of 100 units of ingredients for preparing said component A, the various ingredients and their mass units are as follows: PTMEG1000 10 to 20 units; PTMEG2000 25 to 35 units; EP330 30 to 40 units; BDO 6 to 10 units; H20 0.40 to 0.50 units; AK8804 0.70 to 1.30 units; Antifungal agent 0.4 to 0.8 units; BDMAE 0.16 to 0.21 units; T-12 0.016 to 0.021 units; EG 10 to 20 units; APP 4 to 10 units; said component B is a prepolymer formed by stirring and reacting diisocyanate and polytetrahydrofuran ether polyol at 80 to 13 BE2023/5638 100 °C for 4 to 6 hours, having a -NCO value of 12 to 14; based on a total mass of 100 ingredient units for the preparation of said component B, the various ingredients and their mass units are as follows: Diisocyanate 45 to 55 units; Ether polyol 45 to 55 units; polytetrahydrofuran the molar ratio between active -H contained in said component A and the -NCO group contained in component B is 1.00:0.98 to 1.03. 2) A flame retardant and droplet/particle-free polyurethane anti-vibration and sound-absorbing pad according to claim 1, characterized in that in component A, said antifungal agent is a KP-M100 polyurethane antifungal agent produced by Foshan KEPUYIN Company or a M8 polyurethane antifungal agent produced by Dongguan Guangshiyuan Company. 3) Anti-vibration and sound-absorbing pad made of flame-retardant polyurethane and without flaming droplets/particles according to claim 1, characterized in that, based on a total mass of 100 units of ingredients for the preparation of said component A, the various ingredients and their mass units are as follows: PTMEG1000 15 to 18 units; PTMEG2000 25 to 28 units; EP330 32 to 35 units; BDO 8 to 10 units; H20 0.4 to 0.45 units; AK8804 0.8 to 1.2 units; KP-M100 0.4 to 0.6 units; BDMAE 0.17 to 0.19 units; T-12 0.018 to 0.020 units; EG 10 to 14 units; APP 4 to 8 units. 4) Anti-vibration and sound-absorbing pad made of flame-retardant and non-flammable polyurethane 14 BE2023/5638 flaming droplets/particles according to any one of claims 1 to 3, characterized in that, in component A, said EG has a particle size of 100 to 200 mesh and an expansion rate of 250 to 300 mL/g. 5) Anti-vibration and sound-absorbing pad made of flame-retardant polyurethane and without flaming droplets/particles according to any one of claims 1 to 3, characterized in that, in component A, said APP has a particle size of 1,500 to 2,000 mesh. 6) Anti-vibration and sound-absorbing pad made of flame-retardant polyurethane and without flaming droplets/particles according to any one of claims 1 to 3, characterized in that the mass ratio between said EG and said APP in component A is 1:0.35 to 0.45. 7) Anti-vibration and sound-absorbing pad made of flame-retardant polyurethane and without flaming droplets/particles according to claim 1, characterized in that, in component B, said diisocyanate is MDI; said polytetrahydrofuran ether polyol is PTMEG 1000; based on a total mass of 100 ingredient units for the preparation of said component B, the various ingredients and their mass units are as follows: PTMEG1000 45 to 50 units; MDI 50 to 55 units. 8) Anti-vibration and sound-absorbing pad made of flame-retardant polyurethane without flaming droplets/particles according to claim 1, characterized in that the molar ratio between the active -H contained in said component A and the -NCO group contained in component B is from 1.00:0.99 to 1.01. 9) A method of preparing a flame retardant polyurethane anti-vibration and sound-absorbing pad without flaming droplets/particles according to any one of claims 1 to 8, characterized in that said method comprises the following steps: first preheating component A to a temperature of 30 to 34°C and component B to 38 to 40°C; 42°C, then pour in the preheated component A and component B 15 BE2023/5638 preheated in a preheated mold at 60 to 70°C to achieve solidification forming, in order to obtain a flame retardant polyurethane anti-vibration and sound-absorbing pad without flaming droplets/particles. 10) A method of preparing a flame retardant polyurethane anti-vibration and sound-absorbing pad without flaming droplets/particles according to claim 9, characterized in that the solidification forming temperature is 60 to 70°C and the duration is 10 to 15 min.