CN105949493A - Foaming composition and preparation method thereof - Google Patents

Abstract

The invention discloses a foaming composition. The foaming composition comprises, by weight, 1-5 parts of 2, 3-dibromo-1-propylene, 100 parts of 1, 1, 1, 3, 3-pentafluoropropane, 0.5-1 part of tetramethyl guanidine trifluoromethanesulfonate, 10-50 parts of cyclopentane, 1-5 parts of hexafluoro cyclopropane, and 0.5-2 parts of 2, 2, 4-trimethylpentane. The invention also provides a preparation method of the foaming composition. The foaming composition provided by the invention has the advantages of small foam heat conductivity coefficient, low foam density and high foaming efficiency.

Description

A kind of composition, foam and preparation method thereof

Technical field

The present invention relates to foaming agent field, be specifically related to a kind of composition, foam and preparation method thereof.

Background technology

It is zero that 1,1,1,3,3-pentafluoropropane is called for short HFC-245fa, ODP value, is a kind of chemical combination replacing CFC, HCFC Thing.Fluoro trichloromethane (R-11), dichlorodifluoromethane (R-11), a fluorine dichloroethanes (HCFC-141b) can be replaced Purposes, the foaming agent of middle ozone that is used as not damage the ozone layer, cold-producing medium, abluent, heat-conduction medium, aerosol push away Enter agent, solvent, power cycle working fluids, fire-extinguishing composite, gaseous electrolysis matter etc..

HFC 245fa is used primarily in novel environment friendly foaming agent.China the most also uses HFC-141b as hard polyurethane Ester foaming agent, by " Montreal Protocol " regulation, the U.S. will disable HFC-141b in 2003, and China is according to " China ODS is phased out national scheme " regulation the superseded time of HFC-141b was advanced to by the year two thousand forty The year two thousand thirty.The factory of US and European each foam plastics industry starts to turn to the succedaneum not consuming ozone the most comprehensively. Compared with the foaming agent such as HFC 245fa with HFC-141b, pentane, there is relatively low boiling point and higher vapour pressure, can change The mobility of kind foaming process foam material, prepared foam has preferable cryogenic property.And because its boiling point is low, it is possible to provide Wider operating procedure scope, is the following optimum selection substituting CFC.

CN1541261 provides azeotrope-like group of 1,1,1,2-tetrafluoroethane, 1,1,1,3,3-pentafluoropropane and 2-methybutane Compound, said composition meets environmental requirement and is used as cryogen, aerosol propellant, metered dose inhaler, polymer bubble Foam body foaming agent, heat transfer medium and gaseous dielectric medium.

CN02827976 provides containing pentafluoropropane, selected from the second of Decafluoropentane, perfluorobutyl methyl ethers and combinations thereof Component and the compositions of the 3rd component selected from methanol, 1,2-Trans-dichloroethylene and combinations thereof.Additionally provide containing this The cold-producing medium of bright compositions, foaming agent, foam composition, polyol premixes, closed cell foamed plastic, combination can be sprayed Thing etc..

CN02807084 provides 1,1,1,3, the 3-pentafluoropropane being used as intermediate in the production of HFC-245fa And the azeotropic of 1-chloro-1,1,1,3,3,3-pentafluoropropane (HCFC-235fa) and Azeotrope-like mixtures (HFC-245fa).Also provide A kind of method separating HFC-245fa and HCFC-235fa.HFC-245fa can serve as nontoxic zero ozone depletion Fluorocarbons, this fluorocarbons can serve as solvent, foaming agent, cryogen, cleaning agent, smog propellant, biography Thermal medium, gaseous dielectric medium, fire-extinguishing composite and power cycle working fluids.

The existing compositions containing HFA 134a is made foaming agent and is used, and polyurethane foam heat conductivity is higher, poly-ammonia Ester foam density is higher, has influence on its life-time service prospect as foaming agent.

Summary of the invention

The technical problem to be solved in the present invention is the defect overcoming prior art, it is provided that a kind of foam thermal conductivity is low, foam Density is little, composition, foam that bubbling efficiency is high and preparation method thereof.

In order to solve above-mentioned technical problem, the present invention is achieved by the following technical solutions: a kind of composition, foam, presses Parts by weight, consisting of:

The present invention also provides for the preparation method of this composition, foam, comprises the following steps:

(a) premixing

By proportioning by 1-5 part 2,3-bis-bromo-1-propylene, 100 part 1,1,1,3,3-pentafluoropropane, 10-50 part Pentamethylene., 0.5-2 Part pure isooctane, 1-5 part hexafluorocyclopropane, 0.5-1 part tetramethyl guanidine trifluoro-methanyl sulfonate, in temperature 0～10 DEG C with liquid condition premixing 10-35h, obtain intermediate products；

B () hydrogen fluoride gas bubbling mixes

The intermediate products that step (a) obtained add in bubbling reactor, then are passed through hydrogen fluoride gas and carry out bubbling mixing 1-5h, obtains final products.

Described 1,1,1,3,3-pentafluoropropane is preferably 1:5-10 with the mass ratio of hydrogen fluoride gas.

Heretofore described tetramethyl guanidine trifluoro-methanyl sulfonate (C₆H₁₄F₃N₃O₃S), commercially available acquirement, as adopted The product produced with Chinese Academy of Sciences's Lanzhou Chemical Physics institute；2,3-bis-bromo-1-propylene, commercially available acquirement, as usedHundred Ling Wei Science and Technology Ltd.The product produced；1,1,1,3,3-pentafluoropropane, commercially available acquirement, as used Ju Hua group The product that company limited produces；Pentamethylene., commercially available acquirement, as usedEast, Anhui Pentamethylene. chemical industry Limited Liability Company；Pure isooctane, commercially available acquirement, as can use Chengdu moisten native country Chemical Co., Ltd. produce product Product.

Heretofore described bubbling reactor, commercially available acquirement, as used the Hebei China Tech limited public affairs of strong scientific and technological development The product that department produces.

Compared with prior art, the method have the advantages that

When 1, using the compositions foaming of the present invention, polyurethane foam heat conductivity is low, in the composition, foam of the present invention, 2,3-bis-bromo-1-propylene, Pentamethylene., tetramethyl guanidine trifluoro-methanyl sulfonate mix homogeneously, Pentamethylene. and system have good Dissolubility and diffusibility, make polyurethane foam heat conductivity lower, and heat conductivity is at 0.021W (m K)^-1Below；

When 2, using the compositions foaming of the present invention, polyurethane foam combustibility is low, and 2,3-bis-bromo-1-propylene have fire retardation, Effectively reduce the combustibility of pentafluoropropane compositions；

When 3, using the compositions foaming of the present invention, polyurethane foam density is low, uses the mixing of hydrogen fluoride gas bubbling, both Can improve mixed effect, the fluohydric acid gas of oligodynamical can also improve bubbling efficiency, makes polyurethane foam density reduce, Foam density is at 47.8kg m^-3Below.

Detailed description of the invention

Below in conjunction with specific embodiment, the present invention is further detailed, but the invention is not limited in described enforcement Example.

Raw material described in embodiment and the most commercially available acquirement of equipment, wherein part material and description of equipment are as follows:

Tetramethyl guanidine trifluoro-methanyl sulfonate (C₆H₁₄F₃N₃O₃S): purchased from Chinese Academy of Sciences's Lanzhou Chemical Physics institute；

2,3-bis-bromo-1-propylene: be purchased fromLark prestige Science and Technology Ltd.；

1,1,1,3,3-pentafluoropropane: purchased from Juhua Group Co., Ltd.；

Pentamethylene.: be purchased fromEast, Anhui Pentamethylene. chemical industry Co., Ltd；

2,2,4-trimethylpentane: moisten native country Chemical Co., Ltd. purchased from Chengdu；

Bubbling reactor: purchased from the strong Science and Technology Development Co., Ltd. of Hebei China Tech.

Embodiment 1

A kind of composition, foam, by weight, formula is as follows:

Preparation method comprises the following steps:

Step (1) premixing

In 500L stirring-type reactor, by proportioning by 3 part 2,3-bis-bromo-1-propylene, 100 part 1,1,1,3,3-five fluorine third Alkane, 30 parts of Pentamethylene., 2 parts of hexafluorocyclopropane, 1 part of pure isooctane, 0.6 part of tetramethyl guanidine fluoroform sulphur Hydrochlorate, temperature 5 DEG C with liquid condition premixing 10h, obtains intermediate products.

Step (2) hydrogen fluoride gas bubbling mixes

Intermediate products step (1) obtained add in 500L bubbling reactor, are passed through 700 parts of hydrogen fluoride gas and carry out Bubbling mixing 5h, makes compositions mix evenly, and hydrogen fluoride gas reclaims, and obtains final products.Numbered WN-1.

Embodiment 2

A kind of composition, foam, by weight, formula is as follows:

Preparation method comprises the following steps:

Step (1) premixing

In 500L stirring-type reactor, by proportioning by 1 part 2,3-bis-bromo-1-propylene, 100 part 1,1,1,3,3-five fluorine third Alkane, 10 parts of Pentamethylene., 1 part of hexafluorocyclopropane, 0.5 part of pure isooctane, 0.5 part of tetramethyl guanidine fluoroform Sulfonate, temperature 0 DEG C with liquid condition premixing 20h, obtains intermediate products.

Step (2) hydrogen fluoride gas bubbling mixes

Intermediate products step (1) obtained add in 500L bubbling reactor, are passed through 500 parts of hydrogen fluoride gas and carry out Bubbling mixing 1h, makes compositions mix evenly, and hydrogen fluoride gas reclaims, and obtains final products.Numbered WN-2.

Embodiment 3

A kind of composition, foam, by weight, formula is as follows:

Preparation method comprises the following steps:

Step (1) premixing

In 500L stirring-type reactor, by proportioning by 5 part 2,3-bis-bromo-1-propylene, 100 part 1,1,1,3,3-five fluorine third Alkane, 50 parts of Pentamethylene., 5 parts of hexafluorocyclopropane, 2 parts of pure isooctane, 1 part of tetramethyl guanidine trifluoromethayl sulfonic acid Salt, temperature 10 DEG C with liquid condition premixing 35h, obtains intermediate products.

Step (2) hydrogen fluoride gas bubbling mixes

Intermediate products step (1) obtained add in 500L bubbling reactor, are passed through 1000 parts of hydrogen fluoride gas and carry out Bubbling mixing 3h, makes compositions mix evenly, and hydrogen fluoride gas reclaims, and obtains final products.Numbered WN-3.

In above-described embodiment 1-3, the weight of every part can choose any weight matched with equipment, such as g, kg etc..

Properties of product are tested

By embodiment 1-3 products obtained therefrom, join in HFC-245fa type spraying polyurethane foam formulation, equivalent substitution HFC-245fa, loads in material-storage jar by the joined premixed systems of table 1 and isocyanates, regulates gauge in proportion, control well The material temperature of premixed systems and isocyanates, is specifying spraying area to carry out spray coating foaming, sampling and measuring assess bubble after foam ripening Foam performance, data are shown in Table 2.

Table 1:HFC-245fa type spraying polyurethane foam formulation

Density presses GB6343 86 standard testing；Compressive strength presses GB8813 88 standard testing；Heat conductivity is pressed GB10295 88 standard testing, sample size is 100cm × 100cm × 5cm.

Table 2: embodiment 1-3 products obtained therefrom Performance comparision

Numbering	Foam density/kg m-3	Heat conductivity/W (m K)-1	Compressive strength/kPa
				WN-1	47.4	0.021	164
WN-2	47.8	0.021	164
				WN-3	47.1	0.020	165
HFC-245fa	48.6	0.024	162

Understanding, embodiment of the present invention 1-3 gained polyurethane foam products, ratio is used alone HFC-245fa, has lower Foam density, higher compressive strength and lower heat conductivity, resultant effect exceedes and is used alone HFC-245fa.

Claims (3)

1. a composition, foam, it is characterised in that by weight, consisting of:

2. the preparation method of the composition, foam described in claim 1, it is characterised in that comprise the following steps:

(a) premixing

By proportioning by 1-5 part 2,3-bis-bromo-1-propylene, 100 part 1,1,1,3,3-pentafluoropropane, 10-50 part Pentamethylene., 0.5-2 Part pure isooctane, 1-5 part hexafluorocyclopropane, 0.5-1 part tetramethyl guanidine trifluoro-methanyl sulfonate, in temperature 0～10 DEG C with liquid condition premixing 10-35h, obtain intermediate products；

B () hydrogen fluoride gas bubbling mixes

The intermediate products that step (a) obtained add in bubbling reactor, then are passed through hydrogen fluoride gas and carry out bubbling mixing 1-5h, obtains final products.

The preparation method of composition, foam the most according to claim 2, it is characterised in that described 1,1,1,3,3-five Fluoro-propane is 1:5-10 with the mass ratio of hydrogen fluoride gas.