CN103788331A

CN103788331A - Polyurethane flame-retardant material and preparation method thereof

Info

Publication number: CN103788331A
Application number: CN201310749375.3A
Authority: CN
Inventors: 蒙献芳; 周子茜; 陆俊行; 马云
Original assignee: GUANGXI JISHUN ENERGY TECHNOLOGY Co Ltd
Current assignee: GUANGXI JISHUN ENERGY TECHNOLOGY Co Ltd
Priority date: 2013-12-31
Filing date: 2013-12-31
Publication date: 2014-05-14

Abstract

The invention discloses a polyurethane flame-retardant material and a preparation method. The polyurethane flame-retardant material is prepared by virtue of the following steps: in the presence of nitrogen, fetching 10-30ml of isophorone diisocyanate and 10-30ml of dehydrated polyether diol to react for 2 hours at 90 DEG C; cooling to 60 DEG C; adding 3-5ml of dimethylolpropionic acid, 3-5ml of 1,4-butanediol, 3-5ml of trimethylolpropane and 3-5ml of 15% boron phenolic acetone liquid, and sequentially adding 1ml of stannous octoate and dibutyltin dilaurate, and reacting for 4 hours; adding 3ml of acetone to adjust the viscosity; continuously reacting until isocyanate does not change; cooling to below 30 DEG C, and adjusting the viscosity with 1ml of acetone; adding 3ml of triethylamine for neutralization for 5 minutes; adding water and emulsifying and dispersing for 3 minutes; performing reduced-pressure distillation to remove acetone to obtain the polyurethane flame-retardant material. The material prepared by the method is smoke-less in the burning process, and the flame-retardant level of the sample can reach the level UL-94V-1 which is a relatively high flame-retardant level.

Description

A kind of polyurethane flame-proof material and preparation method thereof

Technical field

The present invention relates to a kind of polyurethane flame-proof material and preparation method thereof.

Background technology

Urethane (polyurethane, PU) by the hard section of carbamate and polyether chain or soft section of synthetic materials forming of polyester ether chain, it is comparatively comprehensively material of a class performance, weathering resistance, elasticity and the soft or hard section with good physics characteristic, excellence vary with temperature the advantages such as little, can be made into a series of products such as robe rice plastics, rubber, coating, tackiness agent, fiber, synthetic leather water-proof material, is material of construction, finished industrial product wrapping material, furniture seat cushion material and the refrigerating plant material of comparatively popularizing.

But urethane shortcoming is to be easy to burning, when temperature is spent higher than 60, easily softening, when temperature is spent higher than 160, easily decompose spontaneous combustion, while running into naked light or hot flame, will catch fire, and generate dense smoke and feel wronged and act rashly, at present, the flame resistant method of PU material mainly contains three kinds, adds nonactive fire retardant, reactive flame retardant or in PU, introduces the group that thermotolerance is high, improves PU flame retardant resistance.

Because PU material fire savety is poor, inflammable easily aging.Time discharge a large amount of toxic smogs in burning, can make people poisoning and suffocate at short notice.In the actual use of China PU porous plastics, fire failure constantly occurs.If therefore can not solve effectively, effectively the problem of its fire savety, can not find an approach with abundant scientific evidence and solve the fire savety problem in its use procedure, PU porous plastics just cannot obtain large-scale promotion application in China's building energy conservation so.So the problem such as resistance to combustion, fire prevention of urethane foam becomes important topic in the urgent need to address.

Summary of the invention

For the subject matter of the current domestic and international existence in conjunction with hard polyurethane foam heat-insulation system, in conjunction with the progress of current hard polyurethane foam fire protection flame retarding technology, polyurethane heat insulation material reaches GB B1 level or higher fire-protection rating, single interpolation fire retardant technology can not be dealt with problems, and there is the conflicting problem of Polyurethane Thermal Insulation Building Materials fire retardant performance and mechanical property, the present invention adopts high flame retardant resin to carry out modification to combined polyether, improve flame retardant resistance and keep its excellent mechanical property simultaneously, simultaneously in conjunction with adding fire retardant, flame retardant type solidifying agent has proposed a systematized solution.

The invention provides a kind of polyurethane flame-proof material and preparation method thereof.

The present invention is achieved through the following technical solutions:

(1) under nitrogen protection, get the each 10-30ml of polyether Glycols after isophorone diisocyanate and dehydration, at 90 ℃, react 2h, be cooled to 60 ℃;

(2) add dimethylol propionic acid, 1,4-butyleneglycol, TriMethylolPropane(TMP) and 15% the each 3-5ml of boron phenolic aldehyde acetone solution, then add successively 1ml stannous octoate and dibutyl tin dilaurate, reaction 4h, add again 3ml acetone adjusting viscosity, continue to react unchanged to isocyano, cooling is only below 30 ℃;

(3) again with 1ml acetone adjusting viscosity, add in 3ml triethylamine and 5min, the emulsion dispersion 3min that then adds water, underpressure distillation removes acetone, to obtain final product.

Preferably, the present invention realizes by the following method:

Under nitrogen protection, get the each 20ml of polyether Glycols after isophorone diisocyanate and dehydration, at 90 ℃, react 2h, be cooled to 60 ℃;

The each 4ml of boron phenolic aldehyde acetone solution that adds dimethylol propionic acid, BDO, TriMethylolPropane(TMP) and 15%, then adds 1ml stannous octoate and dibutyl tin dilaurate successively, reaction 4h, add again 3ml acetone adjusting viscosity, continue to react unchanged to isocyano, be cooled to below 30 ℃;

With 1ml acetone adjusting viscosity, add in 3ml triethylamine and 5min again, the emulsion dispersion 3min that then adds water, underpressure distillation removes acetone, to obtain final product.

The material that this law makes, smokeless in combustion processes, the fire-retardant rank of sample can reach UL-94V-1 rank, belongs to higher fire-retardant rank.

The material that this law makes, boron bakelite resin is received in polyurethane chain, can increase the water tolerance of urethane, and tensile strength and pendulum-rocker hardness obvious.There is higher flame retardant properties and excellent mechanical property.

embodiment

Embodiment 1

Under nitrogen protection, get the each 10ml of polyether Glycols after isophorone diisocyanate and dehydration, at 90 ℃, react 2h, be cooled to 60 ℃, add dimethylol propionic acid, 1, 4-butyleneglycol, TriMethylolPropane(TMP) and 15% the each 3ml of boron phenolic aldehyde acetone solution, then add successively 1ml stannous octoate and dibutyl tin dilaurate, reaction 4h, add again 3ml acetone adjusting viscosity, continue to react unchanged to isocyano, cooling is only below 30 ℃, 1ml acetone adjusting viscosity again, add in 3ml triethylamine and 5min, then emulsion dispersion 3min adds water, underpressure distillation removes acetone, obtain.

Embodiment 2

Under nitrogen protection, get the each 20ml of polyether Glycols after isophorone diisocyanate and dehydration, at 90 ℃, react 2h, be cooled to 60 ℃, add dimethylol propionic acid, 1, 4-butyleneglycol, TriMethylolPropane(TMP) and 15% the each 4ml of boron phenolic aldehyde acetone solution, then add successively 1ml stannous octoate and dibutyl tin dilaurate, reaction 4h, add again 3ml acetone adjusting viscosity, continue to react unchanged to isocyano, cooling is only below 30 ℃, 1ml acetone adjusting viscosity again, add in 3ml triethylamine and 5min, then emulsion dispersion 3min adds water, underpressure distillation removes acetone, obtain.

Embodiment 3

Under nitrogen protection, get the each 30ml of polyether Glycols after isophorone diisocyanate and dehydration, at 90 ℃, react 2h, be cooled to 60 ℃, add dimethylol propionic acid, 1, 4-butyleneglycol, TriMethylolPropane(TMP) and 15% the each 5ml of boron phenolic aldehyde acetone solution, then add successively 1ml stannous octoate and dibutyl tin dilaurate, reaction 4h, add again 3ml acetone adjusting viscosity, continue to react unchanged to isocyano, cooling is only below 30 ℃, 1ml acetone adjusting viscosity again, add in 3ml triethylamine and 5min, then emulsion dispersion 3min adds water, underpressure distillation removes acetone, obtain.

The fire retardant material that the present invention is made, according to UL94 standard testing, is got 10 samples (2 cover) test.5 samples of each thickness, at 23 ℃, are placed under the condition of 50%RH after 48 hours and are tested.5 samples of each thickness are placed after 7 days and are tested under the condition of 70 ℃.

Samples vertical is placed in major axis, installs.When installation, make one end that sample is lower be placed on sample compared with the centre of low side apart from the blue flame of incendiary pencil top 3/8 " being highly 3/4 ", burn 10 seconds, then remove flame (from sample at least away from 152mm).

If more than ground of sample drip down, one deck that these liquid just drop in below sample does not pass through on the cotton of Surgery Treatment, and this layer of cotton is placed on below sample 12 and " locates.

Through test, embodiment 1-3 all can reach following result:

A: after test flame is taken away, still have flare burning to exceed 30 seconds without any sample.

B: for 5 samples of every cover, after lighting for 10 times, the time altogether of the burning with flare is no more than 250 seconds.

C: burn on fixture always and (include the burning of flare and rubescent burning) without any sample.

D: without any sample, the drop that burning is melted drips and lighted the 12 " cottons of locating below.

E: without any sample, after removing test flame for the second time, continue rubescent burning and exceed 60 seconds.

All meet 94V-1 standard.

Claims

1. a polyurethane flame-proof material, is characterized in that being made by following steps:

(2) add dimethylol propionic acid, 1,4-butyleneglycol, TriMethylolPropane(TMP) and 15% the each 3-5ml of boron phenolic aldehyde acetone solution, then add successively 1ml stannous octoate and dibutyl tin dilaurate, reaction 4h, add again 3ml acetone adjusting viscosity, continue to react unchanged to isocyano, be cooled to below 30 ℃;

2. a polyurethane flame-proof material, is characterized in that making by the following method:

(1) under nitrogen protection, get the each 20ml of polyether Glycols after isophorone diisocyanate and dehydration, at 90 ℃, react 2h, be cooled to 60 ℃;

(2) add dimethylol propionic acid, 1,4-butyleneglycol, TriMethylolPropane(TMP) and 15% the each 4ml of boron phenolic aldehyde acetone solution, then add successively 1ml stannous octoate and dibutyl tin dilaurate, reaction 4h, add again 3ml acetone adjusting viscosity, continue to react unchanged to isocyano, be cooled to below 30 ℃;