CN106928431B - A kind of silicon-based polyurethane foamable composite and preparation method thereof - Google Patents
A kind of silicon-based polyurethane foamable composite and preparation method thereof Download PDFInfo
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- CN106928431B CN106928431B CN201511026727.8A CN201511026727A CN106928431B CN 106928431 B CN106928431 B CN 106928431B CN 201511026727 A CN201511026727 A CN 201511026727A CN 106928431 B CN106928431 B CN 106928431B
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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
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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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
- C08G2101/00—Manufacture of cellular products
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical Kinetics & Catalysis (AREA)
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- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to it is a kind of include the foamable composite with the straight chain organopolysiloxane and polyisocyanates of pendant hydroxyl group, the composition includes: (A) at least one formula (I) the straight chain organopolysiloxane R with pendant hydroxyl group3‑[SiR1R2O‑]m‑SiR1R2‑R3(I) wherein R1、R2And R3Respective expression-R-OH or-R independently of one another, wherein R indicates the C of monovalence1‑C20Alkyl, m be 0-1000 integer, preferably 1-500, more preferably 3-200, particularly 5-20 integer, condition is all R1And R2In at least three expression-R-OH；And (B) at least one polyisocyanates.
Description
Technical field
The present invention relates to a kind of novel silicon-based polyurethane foamable composites and preparation method thereof.Specifically, this hair
It is bright to be related to a kind of including the foamable composite with the straight chain organopolysiloxane and polyisocyanates of pendant hydroxyl group.
Background technique
The production of polyurethane foamed material can be divided into semi-prepolymer process and one-step method.One-step method will be measured comprising poly-
The raw material of ester polyol or polyether polyol and polyisocyanates, which directly pours into mold, to react, and demoulds after curing molding to obtain the final product
To polyurethane foamed material.Semi-prepolymer rule be by a part of polyester polyol or polyether polyol first with it is excessive more
Isocyanates is reacted, and preparation-NCO content is higher and the lower performed polymer of viscosity, then again by them and remainder
Polyurethane foamed material is made in the reactions such as polyester polyol or polyether polyol, foaming agent, catalyst and foam stabilizer.With one-step method
It compares, the production process of semi-prepolymer process is longer and higher cost.
As polyurethane is widely used in each application field, the polyol starting material of synthesis of polyurethane also becomes more and more
Sample.Organopolysiloxane, especially organic silicone oil, as the high-molecular compound of low toxicity, unique Si-O key and Si-C
Key has the characteristics that high bond energy, low cohesive energy.If organopolysiloxane is introduced into polyether polyols, may improve
The structural mechanical property of polyether polyols.
In polyurethane foam industry, silicone oil has become in polyurethane formulations as traditional surfactant to be lacked
Component.And nearest research hotspot goes to from surfactant and studies by the polyurethane foam of main chain of silicone oil.For this
For class polyurethane foam, mechanical performance, especially compressive strength and electric conductivity attract people's attention very much.Also,
For organosilicon, it is considered that due to the presence of its Si-O key, polymer will form inorganic oxygen barrier exhausted in combustion
Thermal-protective coating silica can prevent to a certain extent or inhibit the progress of combustion process, therefore with silicone backbone
Polyurethane is considered as a kind of effective and nontoxic fire proofing, but it usually requires to carry out compounding ability with traditional fire retardant
Embody beneficial flame retardant effect.
Disclosed in CN1643020A a kind of organopolysiloxane including straight chain or branching type and diisocyanate or
The foamable composite of polyisocyanates and foaming agent, wherein the end of the chain of organopolysiloxane at least 95% is by-O-SiR1 2O-
SiR2 2-R3The aminoalkyl or hydroxy alkyl of-Z blocks.The poly- of the straight chain of terminal hydroxyl sealing end has been all made of in embodiment
Siloxanes.When had in the technical solution of the patent using emulsifier, and reacting required mixing in embodiment
Between be 5 minutes.
In addition, CN101405319A discloses a kind of method for preparing organically-modified organopolysiloxane, wherein increasing
Make each molecule that there is at least one to be selected from organic poly- silicon oxygen of the reactive group of aminoalkyl and hydroxyalkyl in the presence of solvent
Alkane with per molecule there is the polyisocyanates of at least two isocyanate groups to react.It is same in the document as organopolysiloxane
Sample uses terminal amino group or hydroxy-end capped linear silicones, and uses semi-prepolymer process to prepare polyurethane foam
Material.It needs to prepare performed polymer first in this method.
Summary of the invention
The purpose of the present invention is therefore that provide a kind of foamable composite, the foam as made from the foamable composite
Material is improved compared to existing polyurethane foamed material flame retardant property.In addition, foamable composite according to the present invention
Also foamed material should be made to be easier to prepare.
The first aspect of the invention is related to a kind of foamable composite, it includes:
(A) the straight chain organopolysiloxane with pendant hydroxyl group of at least one formula (I)
R3-[SiR1R2O-]m-SiR1R2-R3 (I)
Wherein R1、R2And R3Respective expression-R-OH or-R independently of one another,
Wherein R indicates the C of monovalence1-C20Alkyl,
Integer of the m for 0-1000, the integer of preferably 1-500, more preferably 3-200, particularly 5-20,
Condition is all R1And R2In at least three expression-R-OH；
And
(B) at least one polyisocyanates.
In straight chain organopolysiloxane and the prior art such as CN101405319A and CN1643020A according to the present invention
Polysiloxanes is different, it is characterized in that the hydroxyl with side chain, i.e. hydroxyl are flanked on the main chain of polysiloxanes by alkyl.Such as
Fruit can then form cross-linked network knot using the silicone oil with side chain polyhydroxy rather than only with the silicone oil of terminal hydroxy group in system
Structure and the mechanical property for greatly improving polymer, while the anti-flammability of foamed material can also be improved.In addition, using tool of the invention
There is the straight chain organopolysiloxane of pendant hydroxyl group that can also simplify the preparation process of polyurethane foamed material, can especially use
One-step method is prepared and is saved the use of emulsion breaker.
Group R in formula (I) can be aliphatic series, aromatics, alicyclic or heteroaromatic alkyl.One according to the present invention excellent
The embodiment of choosing, the group R in formula (I) are preferably C1-C12Alkyl, such as C1-C12Alkyl or C6-C12Aryl, more
Preferably C1-C8Alkyl, particularly preferably C1-C5Alkyl, such as methyl, ethyl, propyl or butyl.
Advantageously, straight chain organopolysiloxane according to the present invention has at least three, preferably four or more to be located at
The hydroxyl of side chain.Although the both ends for being not precluded within straight chain organopolysiloxane can have hydroxyl, it is preferred that according to the present invention
Straight chain organopolysiloxane only there is pendant hydroxyl group, i.e. R3Do not indicate-R-OH.
Therefore, in a preferred embodiment, all group R1And R2At least three expression-R- independently of each other
OH such as hydroxypropyl, and R3Expression-R such as methyl.
Example as one preferred, one kind according to the present invention preferably have the organopolysiloxane of pendant hydroxyl group such as
Shown in following formula:
Containing hydrogen silicone oil that the straight chain organopolysiloxane that the side chain contains hydroxypropyl can contain hydrogen group by side chain and
Allyl alcohol carries out hydrosilylation under the action of platinum catalyst and is made.The other tools defined for meeting the present invention
Having the straight chain organopolysiloxane of pendant hydroxyl group can also be made in a similar manner.
In scope, in order to obtain above-mentioned improved effect, the content of organopolysiloxane (A) is advantageously made to exist
35 weight %-80 weight %, preferably 40 weight %-70 weight %, more preferable 50 weight %-60 weight %, based on expandable
The total weight of composition.
In scope, for polyisocyanates, all known diisocyanate or polyisocyanate cyanogen can be used
Acid esters, with general formula Q (NCO)n, wherein Q is the aromatics of n function or the alkyl and n of aliphatic series are at least 2 integers.Q is excellent
Choosing has 4-30 carbon atom, and n is preferably not greater than 5 integer.
The diisocyanate that can be used for example has methyl diphenylene diisocyanate (MDI), including crude or technical grade
MDI form and pure 4,4 '-or 2, the MDI of 4 '-isomeric forms or their mixture, and there are also toluene two is different
Cyanate (TDI), naphthalene diisocyanate (NDI), isophorone diisocyanate (IPDI), (1- isocyanate group -1- first of 1,3- bis-
Base ethyl) benzene (TMXDI) or 1,6- hexamethylene diisocyanate (HDI).The polyisocyanates that can be used for example has polymerization
MDI, triphenylmethane triisocyanate or above-mentioned isocyanates biuret or isocyanurate trimer.The polyisocyanate
Cyanate can be used alone or in admixture with one another.
In the present invention, during the foamable composition, pass through organopolysiloxane (A) and optional other
It is reacted with the reactive substance of isocyanate groups with polyisocyanates (B) and forms foamed material.According to the present invention, should
Advantageously make all existing in the isocyanate groups (N=C=O) and composition according to the present invention in polyisocyanates
The molar ratio of OH group is in the range of 0.8-2, preferably 0.9-1.5, more preferable 1-1.3.The OH group may come from
Organopolysiloxane or water or other additives that may be present.The calculating of the molar ratio of NCO/OH is those skilled in the art
Well known to member.For example, when being advantageously only used as comprising organopolysiloxane (A) and water with energy and isocyanate groups in system
When the compound of the OH group of reaction, [NCO] molal quantity/(organic poly- silicon of molar ratio=polyisocyanates (B) of NCO/OH
[OH] molal quantity+2 × [H in oxygen alkane (A)2O] molal quantity).
Foamable composite according to the present invention is preferred in bicomponent system.When preparing bicomponent system, usually
Organopolysiloxane according to the present invention (A) and polyisocyanates (B) is individual as two in two sseparated containers
Component is handled (as stirred and mixing) and storage.When needing to foam, two components are promptly mixed each other before foaming
It closes.Other than the organopolysiloxane (A) and polyisocyanates (B), it can also be added into two kinds of components respectively
He is some to facilitate foaming and stable foam and improves the additive components of other performances.
It, can to of the invention in order to form foamed material for example, a preferred embodiment according to the present invention
Foaming agent is added in composition, foam.The foaming agent can be the mixture of chemical foaming agent or physical blowing agent or both.It is excellent
The chemical foaming agent of choosing is water.Preferred physical blowing agent includes the hydrocarbon of such as low molecular weight, such as propane, butane or pentamethylene,
Dimethyl ether or fluorinated hydrocarbons, such as 1,1- Difluoroethane, HFA 134a or fluoro- 1, the 1- dichloroethanes of 1-.Physical blowing agent
It can be used to that foamed material is assisted to be formed, the even lower foamed material of density thus can be made.With the component A of foamable composite
On the basis of count, the dosage of foaming agent is preferably 0-20 weight %, preferably 5-15 weight %, more preferable 8-13 weight %.
In addition, catalyst can also be contained in foamable composite of the invention.Be suitble to catalyst has such as organotin
Compound, such as dibutyl tin dilaurate, tin dilaurate dioctyl tin, dibutyltin diacetate, two sad dibutyl tins and double
(lauryl mercaptan) dibutyl tin.Also no tin catalyst, such as organic titanate, iron catalyst such as Organic Iron can be used
Close object, organic and inorganic heavy metal compound or tertiary amines.One example of organoiron compound is acetopyruvic acid iron
(III).The example of tertiary amines is triethylamine, tri-n-butylamine, 1,4- diazabicyclo [2.2.2] octane, N, bis- (N, the N- diformazans of N-
Base -2- amino-ethyl) methylamine, N, N- dimethyl cyclohexyl amine, N, accelerine, bis- (N, N- dimethyl aminoethyl) ethers,
N, N- dimethyl -2- ethylaminoethanol, N, N- dimethyl aminopyridine, N, N, N, N- tetramethyl (bis- (2- amino-ethyls)) methylamine,
1,5- diazabicyclo [4.3.0] nonyl- 5- alkene, 11-7- alkene of 1,8- diazabicyclo [5.4.0], N-ethylmorpholine and N,
N, N ', N ", N "-pentamethyldivinyltriamine etc..
Catalyst can use individually or in a manner of mixture.It is preferable to use catalyst mixture, one of catalyst
Mainly promote the pendant hydroxyl group of polysiloxanes and isocyanate group reacts (gel catalyst), and second of catalyst is preferably urged
Change isocyanates reacts (kicker) with water.Suitably select the ratio of two kinds of catalyst in the catalyst mixture can be with
Realize the favorable ratio of foamed material synthesis speed and solidification rate.
It is counted on the basis of the component A of foamable composite, total dosage of catalyst is preferably 0-5.0 weight %, preferably
0.1-3.5 weight %, more preferable 0.3-1.5 weight %.
In many cases, foam stabilizer advantageously can also be added into foamable composite of the invention.For example, available
Foam stabilizer be commercially available siloxane oligomer, through polyether lateral chain modify and can be used to manufacture traditional polyurethane
Ester foamed material.The available commercially available available foam stabilizer of one kind is such as SP 3300, comes from BlueStar Silicone company.
Counted on the basis of the component (A) of foamable composite, foam stabilizer can advantageously with 5 weight % of highest, preferably most
The amount of high 3 weight %, more preferable 0.3-2.5 weight % and particularly preferred 0.7-1.2 weight % use.
As described above, although being not excluded for can according to need using emulsifier, expandable group according to the present invention
It closes and does not preferably contain emulsifier in object.As following Examples is confirmed, have surprisingly discovered that using according to the present invention
Polysiloxanes prepare foamable composite emulsifier-free may be implemented so that preparation method more it is easy and save at
This.
In addition, foamable composite according to the present invention can also optionally include thickener, hole regulator, thixotropic agent,
Plasticizer etc..Can also include fire retardant to further improve anti-flammability, for example, phosphorus-containing compound and the polyester of halogenation and
Polyalcohols or chlorinated paraffin etc..
As a preferred embodiment, carbon nanotube can also be added to foamable composite according to the present invention
In.It has been found that when further addition carbon nanotube, the compressive strength and electric conductivity of foamed material modified in this way
Available further promotion, while can also advantageously improve the distribution and form of abscess.
Counted on the basis of the component (A) of foamable composite, the additive amount of carbon nanotube can 0.1-1.2 weight %,
It is preferred that in the range of 0.1-0.7 weight %.
Carbon nanotube (CNT) is suitable for the invention to be known to the skilled in the art.In the context of the present invention
It is applicable in the definition and description of following carbon nanotube.
Carbon nanotube be from structure a kind of several nanometers of the diameter being made of carbon atom and it is long several microns it is even longer
Hollow tube, each carbon nanotube are basic structure made of a carbon atom passes through sp2 hydridization and three carbon atom bondings of surrounding
It is mainly made of hexagon carbocyclic ring, in addition there are some pentagon carbocyclic rings and heptagon carbocyclic ring.The especially curved CNT of pipe shaft,
There are more pentagon carbocyclic rings or heptagon carbocyclic ring to concentrate on crooked position and makes CNT top closure.According to the graphite flake of composition
The difference of the number of plies, carbon nanotube can be divided into single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube.Carbon nanotube
There are many preparation method, and there are three types of current main preparation methods: arc discharge method, laser evaporization method, chemical vapour deposition technique (are urged
Change decomposition method).In addition there are low temperature solid-state pyrolysismethod, polymer the preparation method, solar energy method, hydrothermal synthesis method, electrolysis method etc..This
A little preparation methods are all familiar to those skilled in the art.
Commercially available oness carbon nanotube product can be used in the application, such as the limited public affairs of Chinese Academy of Sciences's Chengdu organic chemistry
The trade mark of department is the single-walled carbon nanotube of TNST, TNS etc., TND double-walled carbon nano-tube, the multi-walled carbon nanotubes such as TNM1, TNM2.
The second aspect of the invention is related to a kind of method for preparing organic-silicon-modified polyurethane foamed material, including will
The step of all components in foamable composite as described above are mutually mixed.
The third aspect of the invention is related to the straight chain organopolysiloxane with pendant hydroxyl group of formula as described above (I)
Purposes, be used to prepare organic-silicon-modified polyurethane foamed material.
Detailed description of the invention
Fig. 1 is the comparison diagram of the compressive strength of embodiment 1 and embodiment 2.
Fig. 2 is the comparison diagram of the conductivity of embodiment 1 and embodiment 3.
Fig. 3 is the scanning electron microscope (SEM) photograph of polyurethane foamed material made from embodiment 4.
Embodiment
The following raw material is used in all embodiments:
Polysiloxanes (multi-hydroxy silicone oil) with pendant hydroxyl group: BlueStar Silicone, trade mark FLD are come from
50635
Polyether polyol PTMEG-1000: Aladdin is come from, chemical name is polytetrahydrofuran
Carbon nanotube: Chinese Academy of Sciences Chengdu organic chemistry Co., Ltd, trade mark TNM1, multi-walled carbon nanotube are come from
Foam stabilizer: BlueStar Silicone, trade mark SP 3300 are come from
Gel catalyst PC-8: Aladdin is come from, chemical name is N, N- dimethyl cyclohexyl amine
Kicker PC-5: Aladdin is come from, chemical name is N, N, N', N ", N "-pentamethyldivinyltriamine
Physical blowing agent: Honeywell is come from, the trade mark is HCFC-141b, and chemical name is fluoro- 1, the 1- dichloroethanes of 1-
Isocyanates MDI: Aladdin is come from, chemical name is 4,4'- di-2-ethylhexylphosphine oxide (phenyl isocyanate)
Embodiment 1
Prepare organic-silicon-modified polyurethane foamed material according to the present invention
12.4g MDI is added first in the PP plastic cup of 350mL, so that it is melted to liquid under 65 DEG C of environment temperature
And it is cooling in room temperature, as raw material components B.
Then, silicone oil FLD50635 18g, foam stabilizer with pendant hydroxyl group are separately added into the PP plastic cup of 350mL
SP3300 0.14g, gel catalyst PC-8 0.2g, kicker PC-5 0.02g, physical blowing agent HCFC-141b 2g,
Water 0.2g mixes 10s as raw material components A under the stirring of 800rpm.
Raw material components A is poured into raw material components B, at room temperature with 800rpm mixed at high speed 30s, makes its free foaming,
Finally obtain organic-silicon-modified polyurethane foamed material.
Comparative example 1
Prepare conventional polyurethanes foamed material
12.4gMDI is added in the PP plastic cup of 350mL first, so that it is melted to liquid under 65 DEG C of environment temperature
And it is cooling in room temperature, as raw material components B.
Then, polyether polyol PTMEG-1000 30g, foam stabilizer SP3300 are separately added into the PP plastic cup of 350mL
0.14g, gel catalyst PC-8 0.2g, kicker PC-5 0.02g, physical blowing agent HCFC-141b 2g, water 0.2g,
And 10s is mixed under the stirring of 800rpm as raw material components A.
Raw material components A material is poured into raw material components B, at room temperature with 800rpm mixed at high speed 30s, sends out it freely
Bubble, finally obtains polyurethane foamed material.
According to the method for national standard GB2406.2-2009, the oxygen index (OI) of embodiment 1 and comparative example 1 is measured respectively.Implement
The oxygen index (OI) 18.5% of the organic-silicon-modified polyurethane foamed material of example 1, the conventional polyurethanes foamed material of comparative example 1
Oxygen index (OI) be 17%.
Embodiment 2
Prepare the organic-silicon-modified polyurethane foamed material of carbon nano-tube modification
Firstly, the silicone oil FLD50635 18g of side chain polyhydroxy is added in plastic cup.Precise 0.036g carbon nanometer
Pipe, adds it in multi-hydroxy silicone oil；Mixture is moved in water bath sonicator, 30min ultrasonic disperse is carried out；It later will mixing
Object carries out the mechanical stirring of 4h with the revolving speed of 800rpm.
Then, foam stabilizer SP3300 0.14g, gel catalyst PC-8 0.2g, physical blowing agent are added in system
HCFC-141b 2g, water 0.2g mix 10s as raw material components A under the stirring of 800rpm.
Weigh 12.45g MDI makes it melt to liquid and cool down in room temperature under 65 DEG C of environment temperature, as raw material group
Divide B.
Raw material components A is poured into raw material components B, at room temperature with 800rpm mixed at high speed 30s, makes its free foaming,
Finally obtain the organic-silicon-modified polyurethane foamed material of carbon nanotube enhancing.
According to the method for national standard GB8813-2008, the compressive strength of embodiment 1 and 2 sample of embodiment is measured respectively.Implement
The compressive strength of the organic-silicon-modified polyurethane foam of example 1 is 2.28KPa, and the carbon nanotube of embodiment 2 is organic-silicon-modified
The compressive strength of polyurethane foam is 40.6KPa, and the addition of carbon nanotube has increased considerably the compressive strength of foamed material.
Embodiment 3
Prepare the organic-silicon-modified polyurethane foamed material of carbon nano-tube modification
Firstly, the silicone oil FLD50635 18g of side chain polyhydroxy is added in plastic cup.Precise 0.054g carbon nanometer
Pipe, adds it in multi-hydroxy silicone oil；Mixture is moved in water bath sonicator, 30min ultrasonic disperse is carried out；It later will mixing
Object carries out the mechanical stirring of 4h with the revolving speed of 800rpm.
Then, foam stabilizer SP3300 0.14g, gel catalyst PC-8 0.2g, physical blowing agent are added in system
HCFC-141b 2g, water 0.2g, and 10s is mixed as raw material components A under the stirring of 800rpm.
12.45g MDI is weighed, so that it is melted to liquid and is cooled down in room temperature under 65 DEG C of environment temperature, as raw material
Component B.
Raw material components A is poured into raw material components B, in 800rpm mixed at high speed 30s at room temperature, makes its free foaming, most
The silicon-based polyurethane foamed material of carbon nanotube enhancing is obtained afterwards.
Using wideband dielectric impedance spectrometer, at room temperature, the conductivity of embodiment 1 and 3 sample of embodiment is measured respectively, such as
Shown in Fig. 2, the addition of carbon nanotube can increase substantially the electric conductivity of organic-silicon-modified polyurethane foamed material.
Embodiment 4
Prepare the organic-silicon-modified polyurethane foamed material of carbon nano-tube modification
Firstly, side chain multi-hydroxy silicone oil FLD50635 18g is added in plastic cup.Precise 0.072g carbon nanotube,
It adds it in multi-hydroxy silicone oil；Mixture is moved in water bath sonicator, 30min ultrasonic disperse is carried out；Later by mixture
The mechanical stirring of 4h is carried out with the revolving speed of 800rpm.
Then, foam stabilizer SP3300 0.14g, gel catalyst PC-8 0.2g, physical blowing agent are added in system
HCFC-141b 2g, water 0.2g, and 10s is mixed as raw material components A under the stirring of 800rpm.
12.45g MDI is weighed, under 65 DEG C of environment temperature, so that it is melted to liquid and is cooled down in room temperature, as raw material
Component B.
Raw material components A is poured into raw material components B, in 800rpm mixed at high speed 30s at room temperature, makes its free foaming, most
The organic-silicon-modified polyurethane foam of carbon nanotube enhancing is obtained afterwards.
Use the pattern of the organic-silicon-modified polyurethane foamed material of scanning electron microscope observation carbon nanotube.As shown in figure 3, bubble
Pore size distribution is uniform, and abscess is hole-closing structure.
Embodiment 5
It being capable of convenient foam using the straight chain organopolysiloxane according to the present invention with pendant hydroxyl group in order to verify
The preparation of material devises the embodiment.
12.4g MDI is added first in the PP plastic cup of 350mL, so that it is melted to liquid under 65 DEG C of environment temperature
And it is cooling in room temperature, as raw material components B.
Then, silicone oil FLD50635 18g, foam stabilizer with pendant hydroxyl group are separately added into the PP plastic cup of 350mL
SP3300 0.14g, gel catalyst PC-8 0.2g, kicker PC-5 0.02g, water 0.2g, in the stirring of 1500rpm
Lower mixing is used as raw material components A in 5 minutes.
Raw material components A is poured into raw material components B, at room temperature with 1500rpm mixed at high speed 30s, makes its free foaming,
Finally obtain organic-silicon-modified polyurethane foamed material.
The volume of foamed material (is that at least about 4 times of initial volume are defined as by all right foaming of the foamed material
Well), the foamed material with said minuscule hole structure is obtained.
By the embodiment 5 it is found that the two is adopted compared with the conventional scheme disclosed in the embodiment 2 of such as CN1643020A
With the additive component of the same category, difference has side using according to the present invention substantially only in embodiment 5
The straight chain organopolysiloxane of chain hydroxyl.But due to using organopolysiloxane according to the present invention, so that embodiment 5
The foamed material well to foam still can be prepared in the case where not using emulsifier.
Claims (23)
1. a kind of foamable composite, it includes:
(A) at least one formula (I) of the 35 weight %-80 weight % of total weight based on foamable composite has side chain
The straight chain organopolysiloxane of hydroxyl
R3-[SiR1R2O-]m-SiR1R2-R3(I)
Wherein R1、R2And R3Respective expression-R-OH or-R independently of one another,
Wherein R indicates the C of monovalence1-C20Alkyl,
M is the integer of 0-1000,
Condition is all R1And R2In at least three expression-R-OH；
And
(B) at least one polyisocyanates.
2. foamable composite according to claim 1, which is characterized in that m is the integer of 1-500.
3. foamable composite according to claim 1, which is characterized in that m is the integer of 3-200.
4. foamable composite according to claim 1, which is characterized in that m is the integer of 5-20.
5. foamable composite according to claim 1, which is characterized in that group R is C1-C12Alkyl.
6. foamable composite according to claim 5, which is characterized in that group R is C1-C12Alkyl or C6-C12Aryl.
7. foamable composite according to claim 5, which is characterized in that group R is C1-C8Alkyl.
8. foamable composite according to claim 5, which is characterized in that group R is C1-C5Alkyl.
9. according to claim 1 to the foamable composite of 8 any one, which is characterized in that all R1And R2In at least three tables
Show hydroxypropyl.
10. according to claim 1 to the foamable composite of 8 any one, which is characterized in that group R3Do not indicate-R-OH.
11. according to claim 1 to the foamable composite of 8 any one, which is characterized in that the composition also includes carbon nanometer
Pipe.
12. according to claim 1 to the foamable composite of 8 any one, which is characterized in that the isocyanates in polyisocyanates
The molar ratio of all existing OH groups is in the range of 0.8-2 in group and the composition.
13. according to claim 1 to the foamable composite of 8 any one, which is characterized in that the isocyanates in polyisocyanates
The molar ratio of all existing OH groups is in the range of 0.9-1.5 in group and the composition.
14. according to claim 1 to the foamable composite of 8 any one, which is characterized in that the isocyanates in polyisocyanates
The molar ratio of all existing OH groups is in the range of 1-1.3 in group and the composition.
15. according to claim 1 to the foamable composite of 8 any one, which is characterized in that the straight chain organopolysiloxane
Content is in 40 weight %-70 weight %, the total weight based on foamable composite.
16. according to claim 1 to the foamable composite of 8 any one, which is characterized in that the straight chain organopolysiloxane
Content is in 50 weight %-60 weight %, the total weight based on foamable composite.
17. according to claim 1 to the foamable composite of 8 any one, which is characterized in that the composition further includes it
His additive is selected from foam stabilizer, catalyst and foaming agent.
18. according to claim 1 to the foamable composite of 8 any one, which is characterized in that the composition is free of emulsifier.
19. according to claim 1 to the foamable composite of 8 any one, which is characterized in that the composition includes with component
(A) carbon nanotube of meter in the range of 0.1-1.2 weight % on the basis of.
20. according to claim 1 to the foamable composite of 8 any one, which is characterized in that the composition includes with component
(A) carbon nanotube of meter in the range of 0.1-0.7 weight % on the basis of.
21. the method for preparing organic-silicon-modified polyurethane foamed material, including will be according to claim 1 to described in 20 any one
Foamable composite in all components the step of being mutually mixed.
22. method according to claim 21, which is characterized in that be added without emulsifier in this method.
23. according to claim 1 to the straight chain organopolysiloxane with pendant hydroxyl group of formula defined in 20 any one (I)
Purposes, be used to prepare organic-silicon-modified polyurethane foamed material, wherein the amount of the straight chain organopolysiloxane be based on
The 35 weight %-80 weight % of total weight of foamable composite.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1643020A (en) * | 2002-03-21 | 2005-07-20 | 电化学工业有限公司（国际） | Foams containing silicone |
| CN1970598A (en) * | 2005-11-23 | 2007-05-30 | 四川大学 | Preparation of hard polyurethane conductive foam plastic for carbon nanotube filling |
| CN103665826A (en) * | 2012-09-21 | 2014-03-26 | 莫门蒂夫性能材料股份有限公司 | Organosilicone surfactant for producing flexible foam |
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2015
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1643020A (en) * | 2002-03-21 | 2005-07-20 | 电化学工业有限公司（国际） | Foams containing silicone |
| CN1970598A (en) * | 2005-11-23 | 2007-05-30 | 四川大学 | Preparation of hard polyurethane conductive foam plastic for carbon nanotube filling |
| CN103665826A (en) * | 2012-09-21 | 2014-03-26 | 莫门蒂夫性能材料股份有限公司 | Organosilicone surfactant for producing flexible foam |
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