CN110423331A - A kind of water-swellable flexible flame retardant foamed plastics and preparation method thereof - Google Patents
A kind of water-swellable flexible flame retardant foamed plastics and preparation method thereof Download PDFInfo
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- CN110423331A CN110423331A CN201910717250.XA CN201910717250A CN110423331A CN 110423331 A CN110423331 A CN 110423331A CN 201910717250 A CN201910717250 A CN 201910717250A CN 110423331 A CN110423331 A CN 110423331A
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- 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
- C08G18/4829—Polyethers containing at least three hydroxy groups
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- 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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6212—Polymers of alkenylalcohols; Acetals thereof; Oxyalkylation products thereof
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- 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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- 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
- C08J9/009—Use of pretreated compounding ingredients
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- 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
- C08J9/06—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 chemical blowing agent
- C08J9/08—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 chemical blowing agent developing carbon dioxide
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- 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
- C08J9/141—Hydrocarbons
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- 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
- C08J2203/18—Binary blends of expanding agents
- C08J2203/184—Binary blends of expanding agents of chemical foaming agent and physical blowing agent, e.g. azodicarbonamide and fluorocarbon
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/05—Open cells, i.e. more than 50% of the pores are open
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- Chemical & Material Sciences (AREA)
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Abstract
A kind of water-swellable flexible flame retardant foamed plastics, raw material including following parts by weight: 40-60 parts of polyester polyol and/or polyether polyol, 5-10 parts of polyvinyl alcohol/isocyanato silanes coupling agent graft copolymer, 50-90 parts of polyisocyanates, 1-5 parts of pore-creating agents, 0.2-3 parts of foam stabilisers, 5-20 parts of compounding foaming agents, 10-30 parts of modified flame-retardant agent, 0.2-1 parts of catalyst.The preparation method of water-swellable flexible flame retardant foamed plastics is additionally provided simultaneously.Foamed plastics prepared by the present invention introduces polyvinyl alcohol/silane coupling agent graft copolymer on polyurethane foam skeleton, it has been unexpectedly found that, the water suction of gained polyurethane foam, water holding capacity enhancing, the foamed plastics prepared by has better expansion rate of water absorption and resilience, to widen the application field of polyester form；Fire retardant of the present invention is reacted on molecule of the skeleton, forms intrinsic flame-retarded foamed plastic, is avoided fire retardant migration, is precipitated, keeps fire retardation more longlasting, and is influenced on the physical mechanical property of material smaller.
Description
Technical field
The present invention relates to polyurethane foam plastics technical field more particularly to a kind of water-swellable flexible cellular plastic and its
Preparation method.
Background technique
At present there are mainly two types of cable waterproof blocking technologies, one is mechanically-sealing apparatus, such as cable flange flexibility envelope
Block apparatus or air charging system, the second is sealing material class, such as rapid-curing cutback cement, hydro-expansive rubber.
But both blocking technologies have the disadvantage that 1, disassembling operations complexity, can not adapt to cable complicated and changeable and wear
More environment (such as excentral cable or Stranded cable)；2, there is risk of leakage by external force, had after by larger external force permanent
Lose the risk of plugging effect；3, height is required to construction environment temperature, humidity, closure mouth-shaped, complexity small for shape
It blocks mouth and secondary closure mouth plugging effect is bad.
Flexible polyurethane foams refer to that its feature is density with a kind of flexible polyurethane foam plastic of certain elasticity
It is low, resilience is good, ventilative, heat-insulated etc., be widely used in the neck such as furniture production, transportation, building trade, packaging material
Domain.At this stage, flexible polyurethane foams are applied to building structure anti-seep water, the building structure for especially having cable to pass through
The research research and development of body anti-seep water are also seldom.
Chinese patent CN201310402935.8 discloses a kind of water suction flexible polyurethane foams and preparation method thereof, including
Following steps: (1) 40~60 parts of polytetrahydrofuran ether trihydroxylic alcohol, 40~60 parts of polyethylene glycol, hair the preparation of combined polyether: are weighed
2~4 parts of infusion, 0.5~1 part of catalyst and 1~3 part of foam stabiliser, 5~20min of uniform stirring is stand-by at 40~65 DEG C；
(2) 10~30 parts of water absorbent polymer and diisocyanate 30~50 preparation of foamed material: are rapidly added into step (1)
Part, liquid after liquid material whitens, is poured into pre-prepd mold rapidly, makes foam full of mold by timing stirring, quiet
10~30min is set, then is put into 110~120 DEG C of baking ovens and cures 1~2h, cooling and demolding obtains water suction flexibel polyurethane bubble
Foam.The shortcomings that patent is that above-mentioned polyurethane foam expansion rate of water absorption is low, and resilience is poor, as plugging material, blocks mouth
The small destruction polyurethane foam plugging effect that reexpands is poor again.Patent CN201710530908.7 discloses a kind of high water absorption
Property, high-moisture-retention polyurethane foam and preparation method thereof is made of: polyether polyols according to the mass fraction the mixing of following each component
80-120 parts of alcohol, 20-30 parts of diisocyanate, 0.5-55 parts of water-absorbing resins, 20-50 parts of foaming agent, surfactant 0.2-3
Part, 0.2-2 parts of catalyst.The shortcomings that patent is that water-absorbing resins are that polyurethane foam is added in a manner of physical blending
In, if impregnating repeatedly, water-absorbing resins are easy to be lost from the cross-linked network of matrix resin, and the expansion character decline of foam is inhaled
Water, water retention property gradually decrease.Except as described, on polyurethane resin molecule containing flammable hydrocarbon segment, density is small, ratio
Surface area is big, and polyurethane is inflammable, once kindling, combustion process will very quickly, and burning and decomposition generate a large amount of toxic smogs, gives
Fire extinguishing brings difficulty.In addition soft polyurethane foam percent opening is higher, and combustible component is more, when burning due to higher air circulation and
Continuously supply oxygen, it is inflammable and be not easy self-extinguishment.In view of prior art resistance combustion polyurethane foam is mostly that addition type is blended,
The compatibility and its working environment with substrate resin of fire retardant need to develop a kind of polyurethane foam that Intrinsical is fire-retardant modeling
Material.
Summary of the invention
To solve the inflammable not self-extinguishment of polyurethane foam plastics in the prior art, as its expansion rate of water absorption of absorbent foam
Low, resilience is poor, and the defect of water suction, water retention property decline after impregnating repeatedly, it is good that the present invention provides a kind of water-absorbing-retaining performance, can
Reusability, screen resilience is high, and expansion rate of water absorption is high, damage-resistant, intrinsic fire-retardant polyurethane foam plastics, while providing the bubble
The preparation method of foam plastics.Specific technical solution is:
A kind of water-swellable flexible flame retardant foamed plastics, the raw material including following parts by weight:
40-60 parts of polyester polyol and/or polyether polyol
5-10 parts of polyvinyl alcohol/isocyanato silanes coupling agent graft copolymer
50-90 parts of polyisocyanates
1-5 parts of pore-creating agents
0.2-3 parts of foam stabilisers
5-20 parts of compounding foaming agents
10-30 parts of modified flame-retardant agent
0.2-1 parts of catalyst.
Wherein, polyvinyl alcohol/isocyanato silanes coupling agent graft copolymer is and compounds foaming agent, polyester polyol
And/or polyether polyol foaming together with the performed polymer that polyisocyanates is formed under the action of catalyst obtains the chance water
Expanding flexible flame-retarded foamed plastic.
The isocyanato silanes coupling agent is selected from 3- isocyanate propyl triethoxysilane (IPTS) or 3- isocyanide
At least one of sour propyl trimethoxy silicane.
The polyvinyl alcohol/silane coupling agent graft copolymer grafting rate is 15-30%, the polyvinyl alcohol/silane
The alcoholysis degree of the material polyethylene alcohol of coupling agent graft copolymer is 60-88%.
Polyvinyl alcohol/silane coupling agent graft copolymer is the isocyanic acid using hydroxyl and silane coupling agent on polyvinyl alcohol
Group is reacted and is obtained.There is reactive silicon alkoxy on silane coupling agent side chain, hydrolysis occur in the presence of water and generates silanol,
Condensation reaction occurs under suitable conditions between silanol and the hydroxyl of silanol or polyvinyl alcohol, chain and interchain is made to form stereoscopic graticule
The cross-linked structure of network shape.In addition, also remaining a large amount of hydrophilic hydroxyls after polyvinyl alcohol and silane coupling agent reaction, making to be grafted
Copolymer has excellent hydrophilic, absorbent, and in the case where there is water in the external world, hydrone, which penetrates into, contains above-mentioned graft copolymerization knot
Make resin expansion in the polyurethane foam resin of structure, further hydrophilic and gelation becomes water imbibition state.
The polyvinyl alcohol/silane coupling agent graft copolymer preparation method, includes the following steps:
It is ten thousand polyvinyl alcohol of 2.5-3.5 that 100 parts of molecular weight are added into reaction kettle, vacuum dehydration 2-4h at 100-120 DEG C,
It is cooled to 50-70 DEG C, is added in Xiang Shangshu system in 50-70 DEG C of preheated 35-70 part isocyanato silanes coupling
Agent, 100-250 parts of DMSO, temperature control are filtered by vacuum in 50-70 DEG C of sufficiently reaction 3-5h, are dry that grafting crude product, crude product are used
Acetone extraction 24-48h, by insoluble matter in dry to constant weight W in 60 DEG C of vacuum ovens1To get polyvinyl alcohol/silane coupling agent
Graft copolymer.
Polyvinyl alcohol/silane coupling agent graft copolymer grafting rate is calculated according to following formula:
W0For the weight for the polyvinyl alcohol that starting reaction is added.
By controlling the control of the proportion, reaction condition (temperature, time) of reaction mass, the poly- second of regulation gained can be convenient
Enol/silane coupling agent graft copolymer grafting rate also remains a large amount of unreacted hydroxyls on 15-30%, polyvinyl alcohol segments
Base, these hydroxyls are very strong hydrophilic radicals, may also participate in the graft reaction of successive modified fire retardant.
The compounding foaming agent is the compounding of water and physical blowing agent, and wherein the quality proportioning of water and physical blowing agent is 4-
8:1, the physical blowing agent are selected from least one of pentane, isopentane and hexane.
The modified flame-retardant agent is isocyanato silanes coupling agent dry method modification super fine magnesium hydroxide and/or ultra-fine hydrogen-oxygen
Change aluminium to obtain, the isocyanato silanes coupling agent is selected from 3- isocyanate propyl triethoxysilane (IPTS) or 3- isocyanide
It is at least at least one in sour propyl trimethoxy silicane.Magnesium hydroxide and aluminium hydroxide are inorganic fire retardants, and surface is contained greatly
Activity hydroxy is measured, chemical modification can be carried out to change surface and can improve compatibility with polymeric substrate.Magnesium hydroxide or hydrogen
Alumina fire retardant is thermally decomposed, and the heat on comburant surface is absorbed, while the oxygen for discharging water dilute combustion object surface comes eventually
The oxide or good refractory material of generation are decomposed in only combustion reaction, can be improved the ability that polymer resists flame, whole
A fire-retardant process is not only generated without any harmful substance, moreover it is possible to absorb pernicious gas cigarette caused by the burning such as plastics, rubber
Mist is a kind of fire retardant of environmental protection.
The preparation method of modified flame-retardant agent of the present invention includes the following steps:
1) 20 parts of fire retardants are put into drying box, dry 3-5h, the fire retardant after drying are cooled to room at 100-120 DEG C
Warm standby is used；
2) it weighs step 1) obtained flame-retardant agent to be added in high-speed mixer, maintains the temperature at 40-65 DEG C, it is lasting to stir, to
Fire retardant sprays the isocyanato silanes coupling agent of the 1%-2.5% of fire retardant weight, stops stirring after 10-30min and adds
Heat is to get modified flame-retardant agent.
The polyisocyanates includes TDI and/or MDI, is chosen in particular from MDI-100, MDI-50, TDI-80 and TDI-100
At least one of.
The polyester polyol average molecular mass is 3000-6000；And/or the polyether polyol is average opposite
Molecular mass 2000-6500.
Pore-creating agent is usually a kind of special surface activating agent, it has hydrophobicity and hydrophilic segment, its effect is to reduce
The surface tension of foam, promotes cell collapse, improves the percent opening of polyurethane foam plastics, prevents closed pore.Pore-creating agent generally wraps
Include three classes: polypropylene oxide-ethylene oxide copolyether, dimethyl polysiloxane or polyoxygenated alkene-polysiloxanes, institute of the present invention
It states pore-creating agent and preferably uses polyoxygenated alkene-polysiloxanes, can include but is not limited to step figure L-6188, Mei Side with specific example
AK-9901 and Germany win at least one of wound O-501.
The foam stabiliser is one or both of organic foam stabilizer or organic vinyl compound mixture.
It is finer and closely woven uniform that foam stabiliser grows stomata, and hole wall is more stable, and when stomata grows into the thickness of suitable aperture, collaboration is opened
Hole agent aperture.The preferably commercially available B8715LF (German Degussa) of foam stabiliser of the present invention, AK-77001 (dolantin generation
Wound), at least one of L-3002 (U.S. GE).
The catalyst be it is well known in the art prepare catalyst used in polyurethane, including but not limited to organotin, have
Machine bismuth and tertiary ammonia class catalyst it is one or more.It is preferred that dibutyl tin dilaurate, dimethylethanolamine, triethylene two
At least one of amine, isooctyl acid bismuth and lauric acid bismuth.
Optionally, flame-retarded foamed plastic of the present invention further includes other fillers, including but not limited to silica, dioxy
Change at least one of titanium and barium sulfate.
The present invention also provides the preparation methods of water-swellable flexible flame retardant foamed plastics, include the following steps:
1) foam stabiliser, pore-creating agent, modified flame-retardant agent and other fillers are added into high-speed mixer, mix to uniform
It is spare；
2) preparation of performed polymer weighs polyester and/or polyether polyol, in 100-120 DEG C of vacuum dehydration 2-4h, is cooled to
40-50 DEG C, diisocyanate and catalyst are added, uniform stirring 1-3h obtains performed polymer at 70-80 DEG C, and performed polymer is cooling
It is stand-by to 25-50 DEG C；
3) preparation of foamed plastics, be added in performed polymer into step 2) under stirring compounding foaming agent, polyvinyl alcohol/
The mixed material that silane coupling agent graft copolymer and step 1) obtain maintains the temperature at 25-50 DEG C and improves revolving speed stirring, fast
Speed is poured into ready mold, and 5-20min foaming is stood, and is placed into and is cured 1-2h in 60 DEG C of baking ovens, cooling and demolding, i.e.,
Obtain the foamed plastics.
Compared with prior art, the invention has the following advantages:
1. the present invention introduces polyvinyl alcohol/isocyanato silanes coupling agent graft copolymerization on polyurethane foam skeleton
Object, so that water holding capacity enhances after polyurethane foam water suction, while it has been unexpectedly found that prepared polyurethane foam has
Expansion rate of water absorption more better than existing water imbibition polyurethane foam and resilience, so that the application field of polyester form has been widened,
Such as the waterproof field of penetrating cable through wall or crossing pipeline.
2. polyurethane foam water absorbing properties of the present invention are stablized, it can repeatedly absorb water repeatedly, can be recycled, economize on resources.
3. polyurethane foam plastics flame retardant property of the present invention is stablized, fire retardant is after isocyanato silanes are coupling agent modified
Reactive functional groups isocyanate group is increased, this fire retardant is grafted on polyurethane foam skeleton, is formed intrinsic fire-retardant
Polyurethane foam avoids fire retardant migration, is precipitated, keeps fire retardation more longlasting, and influence on the physical mechanical property of material
It is smaller.
4. preparation process of the present invention is simple, easy to operate, it is suitable for industrialized production, and preparation process does not have solvent dirty
Dye, belongs to green syt.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below, but is not limited to the contents of the specification.
If agents useful for same number is parts by weight without specified otherwise.Agents useful for same is the commercially available reagent in this field.
1 polyvinyl alcohol of preparation example/isocyanato silanes coupling agent graft copolymer
Be added into reaction kettle 106.6g molecular weight be 2.5 ten thousand, the polyvinyl alcohol that alcoholysis degree is 70%, vacuum is de- at 20 DEG C
Polyvinyl alcohol is cooled to 60 DEG C by water 2h, is added in Xiang Shangshu system in 60 DEG C of preheated 40g 3- isocyanatopropyls
Trimethoxy silane, 200gDMSO, temperature control are filtered by vacuum in 60 DEG C of sufficiently reaction 4h, are dry that grafting crude product, crude product are used
Acetone extraction 48h removes unreacted small molecule, by insoluble matter in drying in 60 DEG C of vacuum ovens to constant weight 130g, must be grafted
Polyvinyl alcohol/isocyanato silanes coupling agent graft copolymer that rate is 18%.
In a similar way, regulate and control raw material proportioning and reaction time available different grafting ratesPolyvinyl alcohol/different Cyanate base silane coupling agent graft copolymer.
The preparation of 2 modified flame-retardant agent of preparation example
The preparation method of modified flame-retardant agent includes the following steps:
1) 20 parts of aluminium hydroxides are put into drying box, dry 3h, the fire retardant after drying are cooled to room temperature standby at 120 DEG C
With；
2) it weighs aluminium hydroxide obtained by step 1) to be added in high-speed mixer, maintains the temperature at 60 DEG C, continue to stir, to resistance
4, the 4'- '-diphenylmethane diisocyanate of agent sprinkling fire retardant 1.5% is fired, stop stirring after 10min and is heated to get modified resistance
Fire agent.
The preparation of 1 water-swellable flexible flame retardant foamed plastics of embodiment
A kind of water-swellable flexible cellular plastic, the raw material including following parts by weight: 40 parts of average molecular mass are
5500 polyethylene glycol oxide glycerine, 5 parts of polyvinyl alcohol/silane coupling agent graft copolymer, 60 parts of Toluene-2,4-diisocyanates, 4- diisocyanate
Ester, 3 parts step figure L-6188 pore-creating agent, 1 part of figure silicone oil L580 foam stabiliser advanced in years, the compounding foaming of 15 parts of water and pentane composition
Agent, wherein the proportion of water and pentane is 6:1,20 parts of 3- isocyanate propyl triethoxysilane modified aluminium hydroxides, 3 parts of February
Dilaurylate.
Preparation step are as follows:
1) the figure silicone oil L580 foam stabiliser advanced in years of corresponding number in above-mentioned raw materials is added into high-speed mixer, steps figure L-
6188 pore-creating agents, 3- isocyanate propyl triethoxysilane modified aluminium hydroxide, mix to uniform；
2) preparation of performed polymer weighs the polyethylene glycol oxide glycerine and polyvinyl alcohol/silicon that number is corresponded in above-mentioned raw materials
Alkane coupling agent graft copolymer is down to 40 DEG C to temperature in 110 DEG C of vacuum dehydration 2h, adds Toluene-2,4-diisocyanate, 4- diisocyanate
And dibutyl tin dilaurate, uniform stirring 2h obtains performed polymer at 80 DEG C, and performed polymer is cooled to 40 DEG C for use；
3) water and pentane that proportion is 6:1 are added under stirring into step 2) for the preparation of foamed plastics in performed polymer
Compounding foaming agent and the obtained mixed material of step 1), maintain the temperature at 30 DEG C and improve revolving speed stirring, when starting blistering,
It pours into rapidly in ready mold, stands 15min foaming, place into and cure 1-2h in 60 DEG C of baking ovens, cooling and demolding, i.e.,
Obtain the foamed plastics.
Embodiment 2
Other are same as Example 1, and difference is that polyvinyl alcohol/silane coupling agent graft copolymer dosage is 7.5 parts.
Embodiment 3
Other are same as Example 1, and difference is that polyvinyl alcohol/silane coupling agent graft copolymer dosage is 10 parts.
Embodiment 4
Other are same as Example 1, and difference is that polyvinyl alcohol/silane coupling agent graft copolymer grafting rate is 15%.
Embodiment 5
Other are same as Example 1, and difference is that polyvinyl alcohol/silane coupling agent graft copolymer grafting rate is 30%.
Embodiment 6
Other are same as Example 1, and difference is the use of 3- isocyanate propyl triethoxysilane modified aluminium hydroxide
Amount is 10 parts.
Embodiment 7
Other are same as Example 1, and difference is the use of 3- isocyanate propyl triethoxysilane modified aluminium hydroxide
Amount is 30 parts.
Embodiment 8
Other are same as Example 1, and difference is to compound in foaming agent, and the proportion of water and pentane is 4:1.
Embodiment 9
Other are same as Example 1, and difference is to compound in foaming agent, and the proportion of water and pentane is 8:1.
Embodiment 10
Other are same as Example 1, and difference is to compound in foaming agent, and the proportion of water and pentane is 1:1.
Embodiment 11
Other are same as Example 1, and difference is that polyvinyl alcohol/silane coupling agent graft copolymer grafting rate is 10%.
Embodiment 12
Other are same as Example 1, and difference is that polyvinyl alcohol/silane coupling agent graft copolymer grafting rate is 40%.
Comparative example 1
Other are same as Example 1, and difference is to be added without polyvinyl alcohol/silane coupling agent graft copolymer.
Comparative example 2
Other are same as Example 1, and it is unmodified that difference is that polyvinyl alcohol/silane coupling agent graft copolymer replaces with
The polyvinyl alcohol that molecular weight is 2.5 ten thousand, alcoholysis degree is 70%.
Comparative example 3
Other same as Example 1, difference is fire retardant aluminium hydroxide without 3- isocyanates propyl-triethoxysilicane
Alkane is modified.
Application examples
Polyurethane foam prepared by above-described embodiment and comparative example is done into following performance detection, the results are shown in Table 1.
(1) rebound degree reference standard GB/T 6670-2008.
(2) water absorption rate weighs its quality after the bulk material of 100 × 100 × 50mm to be impregnated to 30min in tap water, meter
Calculate water absorbent rate A (absorbing the quality of water and the mass ratio of foamed material).
A=(m1-m0)/m0
In formula: m1、m0The quality (g) of sample and the quality (g) for the preceding sample that absorbs water after respectively absorbing water.
(3) sample of above-mentioned dipped water is placed on the glass plate with 7 ° of horizontal angle and is stood, weighed every for 24 hours by water retention
Its quality calculates water-retaining property B (quality for the water being kept in water-absorbent material and the ratio of foamed material original quality).
B=(m2-m0)/m0
In formula: m2For the quality (g) after 30min is stood after foamed material water suction on a glass.
(4) expansion rate of water absorption measures the length variation of the sample water suction front and back of above-mentioned size, calculates expansion rate of water absorption P.
P=(L3-L2) × 100%/L2
In formula: L3、L2Length respectively after sample water suction and before water suction when drying.
(5) 127 × 13 × 10mm of vertical burn test specimen size, referring to the vertical of ASTM D3801-96 test sample
Combustion rating.
(6) smoke density test carries out smoke density (SDR) survey to 130 × 10 × 10mm of sample referring to ASTM D2843-1993
Examination.
Table 1
As can be seen from Table 1, water-swellable flexible cellular plastic of the present invention has excellent water suction, water holding capacity, water suction
Rate is up to 800% or more, still further it can be seen that foamed plastics of the present invention has particularly preferred expansion rate of water absorption and rebound degree, absorbs water swollen
For swollen rate 60% or more, rebound degree is also up to 63.5%, this performance make the foamed plastics can be applied to penetrating cable through wall or
The waterproof field of crossing pipeline.Polyurethane foam plastics flame retardant property of the present invention is stablized, and vertical burn test reaches V-0 rank,
Fire retardant increases reactive functional groups isocyanate group, this fire retardant grafting after isocyanato silanes are coupling agent modified
On polyurethane foam skeleton, intrinsic fire-retardant polyurethane foam is formed, fire retardant migration is avoided, is precipitated, make fire retardation
It is more longlasting, and the physical mechanical property of material is influenced smaller.
Above-mentioned detailed description is illustrating for one of them possible embodiments of the present invention, the embodiment not to
The scope of the patents of the invention is limited, all equivalence enforcements or change without departing from carried out by the present invention are intended to be limited solely by the technology of the present invention
In the range of scheme.
Claims (10)
1. a kind of water-swellable flexible flame retardant foamed plastics, which is characterized in that the raw material including following parts by weight:
40-60 parts of polyester polyol and/or polyether polyol
5-10 parts of polyvinyl alcohol/isocyanato silanes coupling agent graft copolymer
50-90 parts of polyisocyanates
1-5 parts of pore-creating agents
0.2-3 parts of foam stabilisers
5-20 parts of compounding foaming agents
10-30 parts of modified flame-retardant agent
0.2-1 parts of catalyst
Wherein, polyvinyl alcohol/isocyanato silanes coupling agent graft copolymer is and compounds foaming agent, polyester polyols are pure and mild/
Or to obtain the chance water swollen for polyether polyol foaming together with the performed polymer that polyisocyanates is formed under the action of catalyst
Swollen flexible flame retardant foamed plastics.
2. water-swellable flexible flame retardant foamed plastics as described in claim 1, which is characterized in that the polyvinyl alcohol/isocyanic acid
Isocyanato silanes coupling agent in ester group silane coupling agent graft copolymer is selected from 3- isocyanates propyl-triethoxysilicane
At least one of alkane or 3- isocyanatopropyl trimethoxy silane.
3. water-swellable flexible flame retardant foamed plastics as described in claim 1, which is characterized in that the polyvinyl alcohol/silane is even
The grafting rate for joining agent graft copolymer is 15-30%；And/or the polyvinyl alcohol/silane coupling agent graft copolymer raw material
The alcoholysis degree of polyvinyl alcohol is 60-88%.
4. water-swellable flexible flame retardant foamed plastics as described in claim 1, which is characterized in that the polyvinyl alcohol/silane is even
Connection agent graft copolymer passes through the preparation method included the following steps and obtains:
It is ten thousand polyvinyl alcohol of 2.5-3.5, vacuum dehydration 2-4h at 100-120 DEG C, cooling that 100 parts of molecular weight are added into reaction kettle
To 50-70 DEG C, it is added in Xiang Shangshu system in 50-70 DEG C of preheated 35-70 part isocyanato silanes coupling agent,
100-250 parts of DMSO, temperature control is in 50-70 DEG C of sufficiently reaction 3-5h, vacuum filtration, dry grafting crude product, and crude product is with third
Ketone extracts 24-48h, and insoluble matter is grafted in dry in 60 DEG C of vacuum ovens to constant weight to get polyvinyl alcohol/silane coupling agent
Copolymer.
5. water-swellable flexible flame retardant foamed plastics as described in claim 1, which is characterized in that the compounding foaming agent be water and
The compounding of physical blowing agent, wherein the quality proportioning of water and physical blowing agent be 4-8:1, the physical blowing agent be selected from pentane,
At least one of isopentane and hexane.
6. water-swellable flexible flame retardant foamed plastics as described in claim 1, which is characterized in that the modified flame-retardant agent is isocyanide
The silane coupler modified super fine magnesium hydroxide of perester radical and/or ultrafine aluminium hydroxide, the isocyanato silanes coupling agent choosing
From at least one of 3- isocyanate propyl triethoxysilane (IPTS) or 3- isocyanatopropyl trimethoxy silane.
7. water-swellable flexible flame retardant foamed plastics as described in claim 1, which is characterized in that the polyisocyanates includes
TDI and/or MDI, is chosen in particular from least one of MDI-100, MDI-50, TDI-80 and TDI-100；And/or the polyester
Polyalcohol average molecular mass is 3000-6000；And/or the polyether polyol average molecular mass 2000-
6500。
8. water-swellable flexible flame retardant foamed plastics as described in claim 1, which is characterized in that the pore-creating agent is polyoxyalkylene
Hydrocarbon-polysiloxanes；And/or the foam stabiliser is one of organic foam stabilizer or organic vinyl compound or two
Person's mixture；And/or the catalyst includes the one or more of organotin, organo-bismuth and tertiary ammonia class catalyst, preferably two
At least one of dibutyl tin laurate, dimethylethanolamine, triethylenediamine, isooctyl acid bismuth and lauric acid bismuth.
9. water-swellable flexible flame retardant foamed plastics as described in claim 1, which is characterized in that the water-swellable flexible flame retardant
Foamed plastics further includes other fillers, and other fillers include at least one of silica, titanium dioxide and barium sulfate.
10. the preparation method of water-swellable flexible flame retardant foamed plastics as described in claim any one of 1-9, including walk as follows
It is rapid:
1) foam stabiliser, pore-creating agent, modified flame-retardant agent and other fillers are added into high-speed mixer, mix to uniformly standby
With；
2) preparation of performed polymer weighs polyester and/or polyether polyol, in 100-120 DEG C of vacuum dehydration 2-4h, is cooled to 40-
50 DEG C, diisocyanate and catalyst are added, uniform stirring 1-3h obtains performed polymer at 70-80 DEG C, and performed polymer is cooled to
25-50 DEG C stand-by；
3) compounding foaming agent, polyvinyl alcohol/silane are added under stirring into step 2) for the preparation of foamed plastics in performed polymer
The mixed material that coupling agent graft copolymer and step 1) obtain maintains the temperature at 25-50 DEG C and improves revolving speed stirring, falls rapidly
Enter in ready mold, stand 5-20min foaming, places into and cure 1-2h in 60 DEG C of baking ovens, cooling and demolding is to get institute
State foamed plastics.
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| CN113897050A (en) * | 2021-10-15 | 2022-01-07 | 泉州玺堡家居科技有限公司 | Bamboo charcoal memory cotton and preparation method thereof |
| CN114437534A (en) * | 2022-02-17 | 2022-05-06 | 江苏七巧工艺木制品股份有限公司 | Composite flame-retardant fireproof wooden door and preparation method thereof |
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| CN111533867A (en) * | 2020-05-26 | 2020-08-14 | 中电保力（北京）科技有限公司 | Polyurethane gel foam and preparation method thereof |
| CN113897050A (en) * | 2021-10-15 | 2022-01-07 | 泉州玺堡家居科技有限公司 | Bamboo charcoal memory cotton and preparation method thereof |
| CN114437534A (en) * | 2022-02-17 | 2022-05-06 | 江苏七巧工艺木制品股份有限公司 | Composite flame-retardant fireproof wooden door and preparation method thereof |
| CN114437534B (en) * | 2022-02-17 | 2023-09-22 | 江苏七巧工艺木制品股份有限公司 | Composite flame-retardant fireproof wooden door and preparation method thereof |
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