CN108503789A - A kind of high rebound foam composition of open-cell polyurethane and prepare foam process - Google Patents
A kind of high rebound foam composition of open-cell polyurethane and prepare foam process Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3278—Hydroxyamines containing at least three hydroxy groups
- C08G18/3281—Hydroxyamines containing at least three hydroxy groups containing three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
Abstract
The invention discloses a kind of high rebound foam composition of open-cell polyurethane and prepare foam process, the high rebound foam composition of open-cell polyurethane, including combined polyether component (component A) and isocyanate component (B component), it is characterized in that the organic-silicon-modified Isocyanate prepolymers body of addition in isocyanate component (B component), the mass fraction of silicone portion is 0.5%~5% in organic-silicon-modified Isocyanate prepolymers body, and mass fraction of the silicone portion in B component is 0.001%~0.05% in organic-silicon-modified Isocyanate prepolymers body.Composition of the present invention, organic-silicon-modified Isocyanate prepolymers body are easy to evenly spread in isocyanate component, and store 6 months it is not stratified；The introducing of organic-silicon-modified Isocyanate prepolymers body will not cause the mechanical property of foam and flame retardant property to decline.It is simple to prepare foam process.
Description
Technical field
The invention belongs to polyurethane fields, and in particular to high rebound foam of open pore polyurethane and preparation method thereof.
Background technology
Opening is an important evaluation index of polyurethane high resilience foam.Opening difference can cause foam cell to seal
It closes, internal gas can not be discharged.When showing as difficult die sinking, die sinking in preparation process, foam inside spalling, demoulding are difficult, and
And volume becomes smaller gas to the cold in abscess after demoulding, and leads to foam contraction.It is stiff that foam surface is shown as in terms of foaming properties
It is remarkably decreased with resilience.Conversely, excessively trepanning can then cause foam fabrication process foam stability to decline, leaked at gas vent
Gas, foam locally collapses bubble at gas vent.
The method for improving polyurethane high resilience foam opening at present mainly introduces pore-creating agent in combined polyether, and
Using further assisting in opening abscesses of physical methods such as roll-in, vacuum, injection compressed airs after demoulding.
Patent document US4929646 discloses a kind of polyether polyols alcohol type pore-creating agent, which is characterized as having
There are high ethylene oxide (EO) ratio, EO ratios to be up to 65%-80%.Pore-creating agent EO ratios are in patent document CN105315448A
75%-83%.Such pore-creating agent Technical comparing is ripe, and the product of existing commercialization is the pore-creating agent being commonly used in the industry.
But the addition of such pore-creating agent can cause the mechanical property of foam and flame retardant property to decline (chemical propellant and macromolecule material
Material, 2016,14 (6)：69-71), and due to EO units have hydrophily, when its in polyether polyol when there are a lot, meeting
Lead to water resistance and hydrothermal stability variation (chemical propellant and high molecular material, 2017,15 (5) of polyurethane (PU) product：
8-19), the main body polyether polyol of high rebound foam is high propylene oxide (PO) structure, the pore-creating agent phase with high EO structures in addition
Dissolubility is poor, and the hydrophily difference of EO and PO, and the high rebound combined polyether meeting partial hierarchical for causing long-time to be placed, top is under
The combined polyether moisture and trepanning agent content in portion are not exactly the same, take upper and lower part combined polyether to foam respectively, in technique table
Now there is bigger difference in terms of product properties.
Patent document US2007072951 discloses a kind of surfactant, and structure is the dimethyl silica containing hydroxyl
Alkane, and hydroxyl is directly coupled on silicon atom.The surfactant is capable of providing preferable foamed open cell.But polysiloxanes is thin
Water substance, combined polyether viscosity is big and polysiloxanes addition is very small, and uniform and stable dispersion is more difficult.
Invention content
The invention solves first technical problem be to provide a kind of high rebound foam composition of open-cell polyurethane.This is opened
Hole polyurethane high resilience foam composition, combined polyether component (component A) are free of pore-creating agent.
The invention solves second technical problem be to provide a kind of method preparing the high rebound foam of open-cell polyurethane.
To solve first technical problem, the technical scheme is that not changing the high rebound foam combination of conventional polyurethanes
Composition formula, the organic-silicon-modified Isocyanate prepolymers body of addition in isocyanate component (B component), to improve polyurethane high-elastic
The opening of foam.
The present invention provides a kind of high rebound foam composition of open-cell polyurethane, including combined polyether component (component A) and different
Isocyanate component (B component), it is characterized in that the organic-silicon-modified Isocyanate prepolymers of addition in isocyanate component (B component)
Body, the organic-silicon-modified Isocyanate prepolymers body are prepared by following methods：
(1) reactor is added in octamethylcy-clotetrasiloxane and acidic catalyst, two silica of tetramethyl dihydro is then added
Alkane, at 60~80 DEG C, 4~6h of ring-opening polymerization, reaction terminates, cooling, reaction product alkali neutralization to neutrality, washing, mistake
Filter, removing small molecule by-product, obtain the dimethyl silicone polymer of end hydrogen-based sealing end.Rotary Evaporators removing small molecule can be used
By-product, revolving temperature, which is 100~130 DEG C, to be advisable.
(2) by the end hydrogen-based dimethyl silicone polymer obtained in step (1) and allyl amine in H2PtCl6Under catalysis, 50~
3~5h is reacted at a temperature of 60 DEG C, and the dimethyl silicone polymer of Amino End Group sealing end is made.Used catalyst H2PtCl6Dosage is generally
10/1000000ths~the 30 of two kinds of reactant qualities.
(3) product obtained in step (2) is carried out dehydrating, then again with excess isocyanate at 75~85 DEG C
1.5~3h is reacted, organic-silicon-modified Isocyanate prepolymers body is generated.Silicone portion in organic-silicon-modified Isocyanate prepolymers body
Mass fraction be preferably 0.5%~5%.
Mass fraction of the silicone portion in B component is preferably in the organic-silicon-modified Isocyanate prepolymers body
0.001%~0.05%, further preferably 0.005%~0.02%.
Step (1) described acidic catalyst is preferably that concentrated hydrochloric acid, the concentrated sulfuric acid, trifluoromethanesulfonic acid or acid cation exchange tree
One kind and combinations thereof in fat etc., the further preferably concentrated sulfuric acid.Acidic catalyst dosage is generally octamethylcy-clotetrasiloxane
The 1%~3% of quality.Preferably 30~40min of first hybrid reaction, then adds tetramethyl two after acidic catalyst addition system
Hydrogen disiloxane carries out end capping reaction.
As the preferred embodiment of the present invention, the number of the dimethyl silicone polymer of the end hydrogen-based sealing end designed in step (1) is equal
Molecular weight is 500~5000, preferably 800~3000.
Isocyanates described in step (3) can be toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate
(MDI), Carbodiimide-Modified MDI, polymeric MDI, polyether-modified MDI, isophorone diisocyanate (IPDI), hexa-methylene
In diisocyanate (HDI), benzene dimethylene diisocyanate (XDI) or Methylcyclohexyl diisocyanate (HTDI) etc. extremely
Few one kind.Further preferably TDI.
Organic-silicon-modified Isocyanate prepolymers body of the present invention makes an addition in isocyanate component, can be effectively improved poly-
The opening of the high rebound foam of urethane.The advance of the present invention is before being effectively improved the opening of polyurethane high resilience foam
It puts and has the following advantages：(1) organic-silicon-modified Isocyanate prepolymers body is easy to evenly spread in isocyanate component, and stores up
Deposit 6 months it is not stratified；(2) introducing of organic-silicon-modified Isocyanate prepolymers body will not lead to the mechanical property and anti-flammability of foam
It can decline.
The present invention further provides a kind of high rebound foam composition specific formula of open-cell polyurethane, raw material is by two groups of A, B
It is grouped as, includes in parts by mass：
Component A (combined polyether component)：50~100 parts of polyether polyol, 0~50 part of polymer polyatomic alcohol；Catalyst 0.2
~5 parts；1~5 part of foaming agent；Foam stabiliser 0.2~3；0.2~6 part of crosslinking agent.
B component (isocyanate component)：Polyisocyanates and organic-silicon-modified Isocyanate prepolymers body.Wherein polyisocyanic acid
Ester includes TDI, MDI, polymeric MDI or modified MDI etc. and its mixture.It is organic in wherein organic-silicon-modified Isocyanate prepolymers body
Mass fraction of the silicon part in B component is preferably 0.001%~0.05%, further preferably 0.005%~0.02%.
A/B mass ratioes are 100: 30~100: 80.
Preferred polyether polyols alcohol functionalities are 3, and relative molecular mass is 4500~8000, proportion of primary OH groups in terminal hydroxy group
More than 70%.
The graft copolymer of the polymer polyatomic alcohol preferred, polyethers polyalcohol and styrene-acrylonitrile.
The catalyst preferred tertiary amine class；The preferred deionized water of foaming agent；The preferably poly- silica of the foam stabiliser
Alkane copolyether；The preferred alcamine compound of crosslinking agent.
Inventive formulation is reasonable, prepares the raw material A of polyurethane high resilience foam, B component has good storage stability.
Polyurethane high resilience foam prepared by the present invention has good opening, and high EO polyether polyols are generally used with the prior art
Alcohol is compared as high rebound foam prepared by pore-creating agent, has better mechanical property and flame retardant property.
To solve second technical problem, the present invention provides a kind of method preparing the high rebound foam of open-cell polyurethane, wraps
Include following steps：(1) by polyether polyol, polymer polyatomic alcohol, catalyst, foaming agent, foam stabiliser and crosslinking agent based on
Amount mixing and the component A that is uniformly dispersed to obtain, polyisocyanates are mixed and are disperseed by metering with organic-silicon-modified Isocyanate prepolymers body
It is uniformly B component；(2) component A and B component are sufficiently mixed uniformly by 100: 30~100: 80 mass ratio and are injected mould temperature and be
In 40~80 DEG C of mold, 2~10min is up to the high rebound foam of open-cell polyurethane for curing.
Specific implementation mode
With reference to embodiments, the present invention will be described in further detail.
The preparation of organic-silicon-modified Isocyanate prepolymers body：
Embodiment 1
(1) it weighs in 100g octamethylcy-clotetrasiloxanes to the three-necked flask with thermometer and condensation reflux unit, rises
Temperature is added the 3.0g concentrated sulfuric acids, is stirred to react 30min, adds 12.1g tetramethyldihydrogendisiloxanes, at 60 DEG C to 60 DEG C
It is stirred to react 5h, reaction terminates, and is cooled to room temperature, with sodium bicarbonate neutralization reaction liquid to neutrality, washes, and filtering is steamed with rotation
Small molecule by-product is evaporated off in 130 DEG C of backspins in hair instrument, rotates 4h, is filtered under diminished pressure, and the end hydrogen that number-average molecular weight is 1200 is made
The dimethyl silicone polymer of base sealing end.
(2) dimethyl silicone polymer and 4.7g allyl amines for weighing the end hydrogen-based sealing end that 50g steps (1) obtain are added instead
It answers in device, is warming up to 50 DEG C, 0.001g H are added2PtCl6Catalyst reacts 4h, and the polydimethylsiloxanes of Amino End Group sealing end are made
Alkane.
(3) dimethyl silicone polymer for the Amino End Group sealing end that step (2) obtains first is heated to 120 DEG C, decompression dehydration 2h,
For use.100g TDI are added into reactor, then plus 1.0g is dehydrated the dimethyl silicone polymer that Amino End Group blocks, control reaction
Temperature reacts 2h at 75~85 DEG C, and the content for measuring reaction product NCO is 47.8% to get to organic-silicon-modified isocyanates
Performed polymer 1, wherein silicone portion mass fraction are 0.99%.
Embodiment 2
(1) it weighs in 100g octamethylcy-clotetrasiloxanes to the three-necked flask with thermometer and condensation reflux unit, rises
Temperature adds the 3.0g concentrated sulfuric acids, is stirred to react 30min to 60 DEG C, adds 7.0g tetramethyldihydrogendisiloxanes, at 60 DEG C
It is stirred to react 5h, reaction terminates, and is cooled to room temperature, with sodium bicarbonate neutralization reaction liquid to neutrality, washes, and filtering is steamed with rotation
Small molecule by-product is evaporated off in 130 DEG C of backspins in hair instrument, rotates 4h, is filtered under diminished pressure, and the end hydrogen that number-average molecular weight is 2000 is made
The dimethyl silicone polymer of base sealing end.
(2) dimethyl silicone polymer and 2.8g allyl amines for weighing the end hydrogen-based sealing end that 50g steps (1) obtain are added instead
It answers in device, is warming up to 50 DEG C, 0.001g H are added2PtCl6Catalyst reacts 4h, prepares the polydimethylsiloxanes of Amino End Group sealing end
Alkane.
(3) dimethyl silicone polymer for the Amino End Group sealing end that step (2) obtains first is heated to 120 DEG C, decompression dehydration 2h,
For use.100g TDI are added into reactor, then plus 1.0g is dehydrated the dimethyl silicone polymer that Amino End Group blocks, control reaction
Temperature reacts 2h at 75~85 DEG C, and the content for measuring reaction product NCO is 47.8% to get to organic-silicon-modified isocyanates
Performed polymer 2, wherein silicone portion mass fraction are 0.99%.
Embodiment 3
(1) it weighs in 100g octamethylcy-clotetrasiloxanes to the three-necked flask with thermometer and condensation reflux unit, rises
Temperature is added the 3.0g concentrated sulfuric acids, is stirred to react 30min, adds 20.0g tetramethyldihydrogendisiloxanes, at 60 DEG C to 60 DEG C
It is stirred to react 5h, reaction terminates, and is cooled to room temperature, with sodium bicarbonate neutralization reaction liquid to neutrality, washes, and filtering is steamed with rotation
Small molecule by-product is evaporated off in 130 DEG C of backspins in hair instrument, rotates 4h, is filtered under diminished pressure, and the end hydrogen-based that number-average molecular weight is 800 is made
The dimethyl silicone polymer of sealing end.
(2) dimethyl silicone polymer and 7.2g allyl amines for weighing the end hydrogen-based sealing end that 50g steps (1) obtain are added instead
It answers in device, is warming up to 50 DEG C, 0.001g H are added2PtCl6Catalyst reacts 4h, prepares the polydimethylsiloxanes of Amino End Group sealing end
Alkane.
(3) dimethyl silicone polymer for the Amino End Group sealing end that step (2) obtains first is heated to 120 DEG C, decompression dehydration 2h,
For use.100g TDI are added into reactor, then plus 1.0g is dehydrated the dimethyl silicone polymer that Amino End Group blocks, control reaction
Temperature reacts 2h at 75~85 DEG C, and the content for measuring reaction product NCO is 47.7% to get to organic-silicon-modified isocyanates
Performed polymer 3, wherein silicone portion mass fraction are 0.99%.
The preparation of the high rebound foam of open-cell polyurethane：
(1) polyether polyol, catalyst, foaming agent, foam stabiliser, crosslinking agent are added by mass parts shown in table 1 and are held
It in device, is thoroughly mixed and is uniformly dispersed, obtain component A, be labeled as A-0；
Wherein polyether polyol be can Leah polyalcohol (Nanjing) Co., Ltd production KPX KE-810, catalyst be U.S.
State's Air Products Company33LX∶BL11=3: 1, foaming agent is deionized water, foam stabiliser
The DC6070 of U.S.'s Air Products Company is selected, crosslinking agent is triethanolamine.
Each material quality number in 1 component A of table
| Raw material | Mass fraction |
| Polyether polyol | 100 |
| Catalyst | 0.6 |
| Foaming agent | 4.0 |
| Foam stabiliser | 1.0 |
| Crosslinking agent | 1.0 |
| It is total | 106.6 |
106.6 mass parts A-0 are added the high EO contents polyether polyols alcohol type pore-creating agent of 1.5 mass parts, are thoroughly mixed point
It dissipates uniformly, obtains component A, be designated as A-1；
Wherein high EO contents polyether polyols alcohol type pore-creating agent selects the CHK- of Jiangsu Changhua Polyurethane Technology Co., Ltd.
350D。
(2) TDI, polymeric MDI and organic-silicon-modified Isocyanate prepolymers body are added to the container by mass parts shown in table 2,
It is thoroughly mixed and is uniformly dispersed, obtain B component；
Wherein TDI is the T-80 of Cangzhou great Hua limited liability companies, and polymeric MDI is Shanghai Huntsman Polyurethanes Co., Ltd
5005, organic-silicon-modified Isocyanate prepolymers body come from embodiment 1-3.
Each material quality score in 2 B component of table
| TDI/% | Polymeric MDI/% | Organic-silicon-modified Isocyanate prepolymers body/% | B component marks |
| 69.0 | 30.0 | 1.0 parts of performed polymers 1 | B-1 |
| 68.8 | 30.0 | 1.2 parts of performed polymers 2 | B-2 |
| 69.2 | 30.0 | 0.8 part of performed polymer 3 | B-3 |
70.0 parts of TDI are uniformly mixed with 30.0 parts of polymeric MDIs, are designated as B-0.
(3) free foaming
B component in mass ratio 100: 42 obtained by component A obtained by (1) and (2) is quickly sufficiently mixed uniformly, Format is used in combination
FPM2 type foam raising instrument records foaming process, and freely steeps deflection ratio by the calculating of foaming curve.
(4) molding foaming
B component in mass ratio 100: 42 obtained by component A obtained by (1) and (2) is quickly sufficiently mixed uniformly and is uniformly injected into
Mould temperature is dies cavity size 380mm*380mm*100mm in 65 DEG C of molds.6min is cured up to polyurethane high resilience foam.
Naturally prepared polyurethane high resilience foam is tested for the property after curing 72h, test result is shown in Table 3.
The opening and performance of 3 foam of table
Component A delamination：A-0,6 months not stratified.There is lamination in 1 week in A-1.
B component delamination：B-0, B-1, B-2, B-3,6 months not stratified.
The center projections height of the deflection ratio of opening free foaming, the jump bubble number of free foaming and molding foaming come
Quantitatively characterizing, deflection ratio is high, jump bubble number expression opening mostly low with center projections height is good.
Tearing strength is tested by GB/T10808-2006, and the oxygen index (OI) of foam is tested by GB/T2406.2-2009.
It can be seen that from table 3 embodiment A, B, C and organic-silicon-modified Isocyanate prepolymers body be used for B component, is prepared by foaming
Polyurethane high resilience foam, have preferable opening.Embodiment A, B, C are compared with the comparative example D for not adding pore-creating agent, power
It learns performance and flame retardant property is not deteriorated.Embodiment A, B, C are compared with the comparative example E for using high EO contents polyether-type pore-creating agent
Compared with the mechanical property and flame retardant property of embodiment A, B, C are superior to comparative example E.And the component A and B component of embodiment A, B, C are equal
Do not occur lamination, and there is lamination after placing 1 week in the component A A-1 of comparative example E.
Above example is only used to illustrate the technical scheme of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
Invention is explained in detail, it will be understood by those of ordinary skill in the art that：It still can be to aforementioned each implementation
Technical solution recorded in example is modified or equivalent replacement of some of the technical features；And these modification or
It replaces, the spirit and scope for various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution.
Claims (10)
1. a kind of high rebound foam composition of open-cell polyurethane, including combined polyether component (component A) and isocyanate component (B
Component), it is characterized in that the organic-silicon-modified Isocyanate prepolymers body of addition, the organosilicon in isocyanate component (B component)
Modified isocyanate performed polymer is prepared by following methods：
(1) reactor is added in octamethylcy-clotetrasiloxane and acidic catalyst, tetramethyldihydrogendisiloxane is then added,
60~80 DEG C, 4~6h of ring-opening polymerization, reaction terminates, cooling, reaction product alkali neutralization to neutrality, and washing, takes off filtering
Except small molecule by-product, the dimethyl silicone polymer of end hydrogen-based sealing end is obtained；
(2) by the end hydrogen-based dimethyl silicone polymer obtained in step (1) and allyl amine in H2PtCl6Under catalysis, 50~60 DEG C
At a temperature of react 3~5h, be made Amino End Group sealing end dimethyl silicone polymer；
(3) product obtained in step (2) is carried out dehydrating, is then reacted at 75~85 DEG C with excess isocyanate again
1.5~3h generates organic-silicon-modified Isocyanate prepolymers body.
2. the high rebound foam composition of open-cell polyurethane according to claim 1, organic-silicon-modified Isocyanate prepolymers body
The mass fraction of middle silicone portion is 0.5%~5%.
3. the high rebound foam composition of open-cell polyurethane according to claim 1, the organic-silicon-modified isocyanates are pre-
Mass fraction of the silicone portion in B component is 0.001%~0.05% in aggressiveness.
4. the high rebound foam composition of open-cell polyurethane according to claim 1, step (1) described acidic catalyst is dense
One kind and combinations thereof in hydrochloric acid, the concentrated sulfuric acid, trifluoromethanesulfonic acid or acid cation exchange resin；Acidic catalyst dosage is eight
The 1%~3% of methyl cyclotetrasiloxane quality.
5. the high rebound foam composition of open-cell polyurethane according to claim 1, it is characterized in that body is added in acidic catalyst
30~40min of first hybrid reaction after system adds tetramethyldihydrogendisiloxane and carries out end capping reaction.
6. the high rebound foam composition of open-cell polyurethane according to claim 1, it is characterized in that poly- the two of end hydrogen-based sealing end
The number-average molecular weight of methylsiloxane is 500~5000.
7. the high rebound foam composition of open-cell polyurethane according to claim 1, the isocyanates described in step (3) are
Toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), Carbodiimide-Modified MDI, polymeric MDI, polyethers
Modified MDI, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), benzene dimethylene diisocyanate
(XDI) or at least one of Methylcyclohexyl diisocyanate (HTDI).
8. the high rebound foam composition of open-cell polyurethane described in a kind of one of claim 1~7, raw material is by two groups of groupings of A, B
At including in parts by mass：
Component A (combined polyether component)：50~100 parts of polyether polyol, 0~50 part of polymer polyatomic alcohol；Catalyst 0.2~5
Part；1~5 part of foaming agent；Foam stabiliser 0.2~3；0.2~6 part of crosslinking agent；
B component (isocyanate component)：Polyisocyanates and organic-silicon-modified Isocyanate prepolymers body；Silicone portion is in B groups
Mass fraction in point is 0.001%~0.05%；
A/B mass ratioes are 100: 30~100: 80.
9. the high rebound foam composition of open-cell polyurethane according to claim 8, the polyether polyols alcohol functionalities are 3,
Relative molecular mass is 4500~8000, and proportion of primary OH groups is more than 70% in terminal hydroxy group；The polymer polyatomic alcohol is that polyethers is more
The graft copolymer of first alcohol and styrene-acrylonitrile；The catalyst is tertiary amines；The foaming agent is deionized water；The bubble
Foam stabilizers are polysiloxane polyether copolymer；The crosslinking agent is alcamine compound；The polyisocyanates be TDI,
MDI, polymeric MDI or modified MDI and its mixture.
10. the method that the high rebound foam composition of open-cell polyurethane described in a kind of one of claim 1~9 prepares foam, packet
Include following steps：(1) by polyether polyol, polymer polyatomic alcohol, catalyst, foaming agent, foam stabiliser and crosslinking agent based on
Amount mixing and the component A that is uniformly dispersed to obtain, polyisocyanates are mixed and are disperseed by metering with organic-silicon-modified Isocyanate prepolymers body
It is uniformly B component；(2) component A and B component are sufficiently mixed uniformly by 100: 30~100: 80 mass ratio and are injected mould temperature and be
In 40~80 DEG C of mold, 2~10min is up to the high rebound foam of open-cell polyurethane for curing.
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| CN113402693A (en) * | 2021-06-29 | 2021-09-17 | 广州亚伊汽车零部件有限公司 | Formula and preparation method of high-resilience foaming material |
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