CN106117491A - Complete water base organic foam material of polyurethane and preparation method thereof - Google Patents

Abstract

The invention belongs to organic high molecular compound preparing technical field, disclose a kind of complete water base organic foam material of polyurethane, A including liquid expects and B expects, A material is 1:1～1.5 with the mass ratio of B material, and wherein A expects that the mass percent of each component is: amino resins 30～40%；Polyester polytrimethylene ether 35～40%；High activity cross-linking agent 1～6%；Silicone oil 0.1～0.8%；Nitrogen phosphorus series non-halogen type fire retardant 15～20%；Catalyst 1～4%；Water 1～3%；B material is isocyanates.Heat-proof quality of the present invention is strong, good stability of the dimension, be difficult to embrittlement and flame retardant effect is good.

Description

Complete water base organic foam material of polyurethane and preparation method thereof

Technical field

The invention belongs to organic high molecular compound preparing technical field.

Background technology

Polyurethane foam plastics is to be primary raw material with polyethers (or PEPA) and polyisocyanates, then adds catalysis Agent, foam stabiliser and foaming agent etc., blended, stirring produces chemical reaction and forms foaming body, can be divided into soft by its hardness Matter and hard two class, wherein RPUF is frequently as construction timber, furniture woods, automotive trim material etc., should Wider by scope.The foaming agent that polyurethane foam plastics often uses in producing has freon foaming agent, alkanes foaming agent, HCFC Class foaming agent, the shortcoming of these foaming agent is: (1) freon has ozone layer destroying effect, along with the increasing of people's environmental consciousness By force, freon is made foaming agent and is the most gradually eliminated；(2) alkanes foaming agent (just mainly having, different, Pentamethylene. etc.) is the easiest Combustion, its explosion hazard becomes the subject matter that foaming system process units faces；(3) HCFC class foaming agent, this kind of substitute Depletion of the ozone layer problem and expensive also can occur.

In view of the shortcoming of existing foaming agent, having risen now a kind of full water foamed technology, principle is water and polyisocyanates Reaction generation CO2, CO2 stay the foaming agent in abscess as foam plastics.Full water foamed full water foamed system ODP value is Zero, nontoxic, safe and environment-friendly, simple process, to equipment without particular/special requirement, low cost, there is not recycling problem, it is not necessary to Investment transformation foaming machine, is ideal foaming technique.

The full water foamed technology of existing employing manufactures polyurethane foam plastics raw material mainly by combined polyether (A material) and Carbimide. Ester (B material) forms, and the mass ratio that A material and B expect is usually 1:1.6～1:1.8, A material and includes expoxy propane/oxirane copolymerization Ether, expoxy propane oxirane copolyether, low degree of functionality polyether polyol, polyhydric alcohol, water, catalyst, surfactant, perforate Agent, cross-linking agent, mill base.The full water foamed preparation method step of this polyurethane foam plastics is: (1) takes expoxy propane epoxy second Alkane copolyether, expoxy propane oxirane copolyether, low degree of functionality polyether polyol, polyhydric alcohol, water, catalyst, surface activity Agent, pore-creating agent, cross-linking agent and mill base, mix in proportion formation A material by above-mentioned material；(2) modified MDI isocyanate is prepared Expect for B；(3) A material and B material being placed in the temperature environment of 20～26 DEG C, proportionally stir mixing, mixing time is 2～5s, Mixing speed is 3500～5000r/min；(4) stirring thing after A material and B material stirring is poured in mould, open behind 3～5min Mould takes out bubble block, obtains polyurethane semi-rigid foam composition.

The shortcoming of technique scheme is: can produce C02, CO2 molecular weight gas time the most full water foamed suitable with air, But molecule is little, easily escaping through the cell wall of hard polyurethane foam, cause the intrinsic pressure reduction of abscess, air molecule is relatively big, penetrates into Abscess speed is relatively slow, causes CO2 faster than the speed that air enters foam hole to the speed of external diffusion from abscess, causes polyurethane foam Foam Material shrinkage, poor dimensional stability；The CO2 produced time the most full water foamed can be partly at the bubble of polyurethane semi-rigid foam material In foam hole, and the thermal conductivity of CO2 is up to 16.3Mw/m.K, and the thermal conductivity of air is 27mWm.K, and the thermal conductivity of air compares CO2 Higher, the heat-proof quality of polyurethane foamed material is poor；The most existing foam stabiliser (i.e. surfactant in formula) pole Property higher, surface activity is relatively low, the foam ultimately formed is relatively big, and the rate of closed hole in foam hole is relatively low, also create a further reduction poly- Urethane foam insulation；4. there is no flame-retardant composition, not there is flame retardant effect, the most common existing equal water of fire retardant Xie Du is higher, be directly used in full water foamed during then can be hydrolyzed, lose anti-flaming function；5. water and carbimide reaction generate CO2 urea bond, and react releasing substantial amounts of heat, heat release causes compositions temperature to raise, when temperature reaches 160 DEG C, CO2 urea bond and Superfluous carbimide crosslinks reaction and generates by-product biuret compounds, and biuret compounds is a kind of rigidity chemical combination Thing, can make polyurethane foamed material overall structure become fragile.The lowest degree of functionality polyether polyol has solvent dilution effect and (i.e. flows Property higher), the viscosity of A material can be greatly lowered, but low degree of functionality polyether polyol is relatively costly, and due to low sense The general hardness of material and dimensional stability that degree compound is made are poor, are difficult to meet customer need.

Summary of the invention

The invention is intended to provide that a kind of heat-proof quality is strong, good stability of the dimension, be difficult to embrittlement and the good poly-ammonia of flame retardant effect The complete water base organic foam material of ester.

The complete water base organic foam material of polyurethane in this programme, the A including liquid expects and B expects, A material and the quality of B material Ratio is 1:1～1.5, and wherein A expects that the mass percent of each component is: amino resins 30～40%；Polyester polytrimethylene ether 35～40%； High activity cross-linking agent 1～6%；Silicone oil 0.1～0.8%；Nitrogen phosphorus series non-halogen type fire retardant 15～20%；Catalyst 1～4%；Water 1 ～3%；B material is isocyanates.

Beneficial effect: in inventive formulation, its Main Function of amino resins is in high temperature of fire environment, can inhale in a large number Receive heat, reduce Heat liberation unit, change simultaneously and decomposite the noble gases such as steam, nitrogen, carbon dioxide, continue to hinder burning The carrying out of reaction, and the degree of functionality of amino resins is relatively up to 5 so that and final product hardness is higher, dimensional stability is high； Polyester polytrimethylene ether 35～40%, is the primary raw material of structure cost product, has good mechanical property, has excellent resistance to high and low Warm nature energy, can in 120 DEG C of temperature ranges life-time service, and the least to its mechanical impact during high and low temperature, nontoxic, tasteless, Wholesomeness is good, has excellent resistance gas and water, oil and abnormal flavour performance；Its Main Function of high activity cross-linking agent is firm product knot Structure, increases its bonding force；Silicone oil its use as foam stabiliser, foam quality can be improved so that foam inside structure is more Add uniformly, thus promote heat-insulating property；Nitrogen phosphorus series non-halogen type fire retardant, as halogen-free type fire retardant, the most in combustion may be used Quickly form charring layer, block burning, and toxic smog in combustion process can be substantially reduced and produce；Catalyst Main Function is Accelerate polyurethane reaction to carry out, and control the structure that polyreaction produces；Water is as response type foaming agent, environmental protection.

The present invention the most suitably reduces A material with B material mass ratio, general control in the range of 1:1～1.4, Carbimide. After the consumption of ester reduces, after water and carbimide reaction generate CO2 urea bond, owing to now isocyanates has been depleted, because of This will not crosslink reaction, hinder the generation of by-product biuret compounds, it is to avoid material embrittlement；It addition, suitably add Enter high activity cross-linking agent, toughness and the bonding force of foam can be increased, select suitable catalyst system, regulation foaming and gel it Between balance, foaming and gel process can be made more flat with the use of triazines catalyst, alkali metal isogel catalyst Surely, the fragility of full water bubble can be improved, strengthen its bonding force to base material.

2. nitrogen phosphorus series non-halogen type fire retardant is selected, i.e. silicon system, phosphorus system and nitrogenated flame retardant according to certain ratio mixing Using, by columbite process, (columbite process refers to that a fire retardant and amino resins, polyester polytrimethylene ether are according to recipe ratio Example mixes, and under 80 DEG C of vacuum environments of temperature, slowly dispersion synthesis two hours, so makes the effective ingredient in fire retardant and ammonia Base resin and polyester polytrimethylene ether generation etherification reaction, form more stable pre-polymerization mixture), the water of this pre-polymerization mixture is steady Qualitative higher, good flame retardation effect.In this three based flame retardant, based on silicon-series five-retardant, phosphorus system, nitrogenated flame retardant are auxiliary, have Machine silicon fire retardant can move to material surface, forms the graded polymer materials that surface is organic silicon fibre retardant enriched layer, once Burning, phosphorus flame retardant can make polymer surfaces rapid dehydration carbonization, produces with silicon-series five-retardant that polysiloxanes is distinctive, contain The inorganic oxygen barrier heat-barrier coating of Si-C key, this had both prevented combustion decomposition product to escape, had inhibited again the heat of macromolecular material Decompose, reached the purposes such as cigarette fire-retardant, low and low toxicity, and the non-flammable gases that nitrogenated flame retardant generates, take away a part of heat Amount, it is possible to decrease the temperature of polymer surfaces, the N2 of generation can capture free radical, the face reaction of suppression high polymer, thus stops Burning.

3. use polarity is relatively low, surface activity is higher silicone oil as foam stabiliser, compare that existing polarity is higher, surface The relatively low foam stabiliser of activity, can obtain thinner, the foam hole of rate of closed hole higher micropore shape, micro-cavernous structure and high Rate of closed hole makes the CO2 in foam hole be difficult to external diffusion, and air is also difficult to enter foam hole, is possible to prevent polyurethane foam material Material shrinks, strengthens its dimensional stability, it is also possible to improve the ability of resistance gas and water, oil and the abnormal flavour of polyurethane foamed material, and Heat-proof quality.It is also added into suitable high activity cross-linking agent, it is possible to improve the fine and closely woven degree in foam hole and overall skeleton hardness, strengthen it Dimensional stability.Further, since the rate of closed hole in foam hole is increased, CO2 is isolated the foam hole closed, the main side of conduction of heat Formula " convection current " conduction heat is just substantially reduced, and polyurethane foamed material is less with the contact area of air, greatly improves poly- The heat-proof quality of urethane foamed materials.

4. A material have selected amino resins and the polyester polytrimethylene ether (degree of functionality is 3) of degree of functionality higher (degree of functionality is 5), Adding appropriate high activity cross-linking agent, add and premixed systems is carried out " secondary synthesis ", the A material viscosity made is the least Reach viscosity in 1000mPa.s (25 DEG C), mental retardation and be less than 400mPa.s (25 DEG C), compare traditional employing low degree of functionality polyethers Polyhydric alcohol is as raw material, and mobility can reach the requirement of full water foamed system, and the raw material of horizontal high functionality prevents from carrying High polyurethane foamed material becomes fragile.

Further, A material is 1:1 with the mass ratio of B material, and wherein A expects that the mass percent of each component is: amino resins 30%；Polyester polytrimethylene ether 35%；High activity cross-linking agent 1%；Silicone oil 0.5%；Nitrogen phosphorus series non-halogen type fire retardant 15%；Catalyst 1%；Water 1%；B material is for isocyanates, and heat-proof quality is strong, good stability of the dimension, be difficult to embrittlement and flame retardant effect is good.

Further, A material is 1:1.5 with the mass ratio of B material, and wherein A expects that the mass percent of each component is: amino resins 40%；Polyester polytrimethylene ether 40%；High activity cross-linking agent 6%；Silicone oil 0.8%；Nitrogen phosphorus series non-halogen type fire retardant 20%；Catalyst 4%；Water 3%；B material is for isocyanates, and heat-proof quality is strong, good stability of the dimension, be difficult to embrittlement and flame retardant effect is good.

Further, A material is 1:1 with the mass ratio of B material, and wherein A expects that the mass percent of each component is: amino resins 37%；Polyester polytrimethylene ether 36%；High activity cross-linking agent 4%；Silicone oil 0.5%；Nitrogen phosphorus series non-halogen type fire retardant 18%；Catalyst 2%；Water 1%；B material is for isocyanates, and heat-proof quality is strong, good stability of the dimension, be difficult to embrittlement and flame retardant effect is good.

Further, ethylenediamine polyether tetrols (i.e. polyethers 403) selected by high activity cross-linking agent, and polyethers 403 is handed over for initiator Connection type polyethers, can reduce the consumption of catalyst after interpolation, cut its product size stability higher.

Further, broad spectrum type silicone oil selected by silicone oil, particularly selects high activity silicon-carbon bond non-hydrolytic type silicone oil, has Excellent combination property, it is adaptable to full water foamed system.

Further, nitrogen phosphorus series non-halogen type fire retardant selects XPM-1000, XPM-1000 to be Monsanto companies of the U.S. The BACN of exploitation, this fire retardant contains higher nitrogen, phosphorus, carbon, can carbonization is also rapidly when running into big fire Expand, form carbonization expanding layer isolation burning things which may cause a fire disaster, stop fire spreading；And owing to it is without halogen, do not produce in carbonisation Raw toxic smoke.

Further, the liquid catalyst containing triethylene diamine selected by catalyst, preferably selects the A-33 of Mai Tu company Catalyst (it contains 33% triethylene diamine), its property miscible with water is good, and such catalyst can promote that isocyanates gathers with polyester Ether reacts, and makes foam cross-link, and gives the mechanical performance that polyurethane foam plastics is good.

The present invention also provides for the preparation method of the complete water base organic foam material of a kind of polyurethane.

The preparation method of the complete water base organic foam material of polyurethane, comprises the steps:

1. amino resins, polyester polytrimethylene ether, high activity cross-linking agent, silicone oil are added in reactor, be heated to being warming up to 80 ℃；

2. aforesaid reaction vessel being carried out evacuation, in question response still, vacuum reaches 0.8MP, and reactor temperature rises to 100～105 DEG C；

3., when reactor temperature drops to 80 DEG C naturally, nitrogen phosphorus series non-halogen type fire retardant is added；

4., when reactor temperature drops to 60 DEG C naturally, catalyst is added；

5., when reactor temperature drops to less than 50 DEG C naturally, after adding water and stirring 0.5h, it is cooled to room temperature；

6. the raw material in reactor and isocyanates are added in injection machine, foamable reaction in the mould of injection machine, Material molding after hardening.

Beneficial effect: step 1. middle amino resins, polyester polytrimethylene ether, high activity cross-linking agent, silicone oil are the most slowly , there is etherification reaction in dispersion；Step 3. in after nitrogen phosphorus series non-halogen type fire retardant mixes with amino resins, polyester polytrimethylene ether, in temperature Spend under 80 DEG C of vacuum environments, slowly dispersion synthesis two hours, so make effective ingredient in nitrogen phosphorus series non-halogen type fire retardant with Amino resins, polyester polytrimethylene ether generation etherification reaction, form more stable pre-polymerization mixture, and the water of this pre-polymerization mixture is steady Qualitative higher.By columbite process, this method makes that flame retardant effect is preferable, heat-proof quality strong, good stability of the dimension and not The easily complete water base organic foam material of polyurethane of embrittlement.

Detailed description of the invention

Below by detailed description of the invention, the present invention is further detailed explanation:

Embodiment one

Each component of the complete water base organic foam material of polyurethane is as follows:

Sequence number	Quality (g)
		Amino resins	30
Polyester polytrimethylene ether	35
		Ethylenediamine polyether tetrols	1
Silicone oil	0.5
		XPM-1000	15
A-33 catalyst	1
		Water	1
Isocyanates	125.25

Embodiment two

Each component of the complete water base organic foam material of polyurethane is as follows:

Sequence number	Quality (g)
		Amino resins	40
Polyester polytrimethylene ether	40
		Ethylenediamine polyether tetrols	6
Silicone oil	0.8
		XPM-1000	20
A-33 catalyst	4
		Water	3
Isocyanates	113.8

Embodiment three

Each component of the complete water base organic foam material of polyurethane is as follows:

Embodiment four

Prepare raw material according to embodiment one or embodiment two or embodiment three, be prepared as steps described below:

1. amino resins, polyester polytrimethylene ether, ethylenediamine polyether tetrols, silicone oil are added in reactor, be heated to being warming up to 80℃；

2. aforesaid reaction vessel being carried out evacuation, in question response still, vacuum reaches 0.8MP, and reactor temperature rises to 100～105 DEG C；

3., when reactor temperature drops to 80 DEG C naturally, nitrogen phosphorus series non-halogen type fire retardant (i.e. XPM-1000) is added；

4., when reactor temperature drops to 60 DEG C naturally, A-33 catalyst is added；

5., when reactor temperature drops to less than 50 DEG C naturally, after adding water and stirring 0.5h, it is cooled to room temperature；

6. the raw material in reactor and isocyanates are added in injection machine, foamable reaction in the mould of injection machine, Material molding after hardening.

Fire retardancy test data

The test specimen of 6 pieces of 254*200*20 (mm) is made, according to GB8624-2012 " construction material and system according to embodiment four Product classification system for fire performance " carry out construction material and the test of product burns grading performance, test result reaches GB8624-2012 standard The requirement (i.e. electrical equipment, article of furniture foam plastics) of B1 level, flame retardant effect is fine.Concrete data are as follows:

The protection domain that this application claims should be as the criterion with the content of its claim, the detailed description of the invention in description May be used for explaining the content of claim Deng record.

Claims (9)

1. the complete water base organic foam material of polyurethane, the A including liquid expects and B expects, it is characterised in that: A material and the mass ratio of B material For 1:1～1.5, wherein A expects that the mass percent of each component is: amino resins 30～40%；Polyester polytrimethylene ether 35～40%；High alive Property cross-linking agent 1～6%；Silicone oil 0.1～0.8%；Nitrogen phosphorus series non-halogen type fire retardant 15～20%；Catalyst 1～4%；Water 1～3%； B material is isocyanates.

The complete water base organic foam material of polyurethane the most according to claim 1, it is characterised in that: the matter that described A material is expected with B Amount ratio is 1:1.5, and wherein A expects that the mass percent of each component is: amino resins 30%；Polyester polytrimethylene ether 35%；High activity cross-links Agent 1%；Silicone oil 0.5%；Nitrogen phosphorus series non-halogen type fire retardant 15%；Catalyst 1%；Water 1%；And B material is isocyanates.

The complete water base organic foam material of polyurethane the most according to claim 1, it is characterised in that: the matter that described A material is expected with B Amount ratio is 1:1, and wherein A expects that the mass percent of each component is: amino resins 40%；Polyester polytrimethylene ether 40%；High activity cross-linking agent 6%；Silicone oil 0.8%；Nitrogen phosphorus series non-halogen type fire retardant 20%；Catalyst 4%；Water 3%；It is isocyanates for B material.

The complete water base organic foam material of polyurethane the most according to claim 1, it is characterised in that: the matter that described A material is expected with B Amount ratio is 1:1, and wherein A expects that the mass percent of each component is: amino resins 37%；Polyester polytrimethylene ether 36%；High activity cross-linking agent 4%；Silicone oil 0.5%；Nitrogen phosphorus series non-halogen type fire retardant 18%；Catalyst 2%；Water 1%；And B material is isocyanates.

5. according to the complete water base organic foam material of polyurethane described in claim 1 or 2 or 3, it is characterised in that: described high activity Ethylenediamine polyether tetrols selected by cross-linking agent.

The complete water base organic foam material of polyurethane the most according to claim 5, it is characterised in that: wide spectrum selected by described silicone oil Type silicone oil.

The complete water base organic foam material of polyurethane the most according to claim 6, it is characterised in that: described nitrogen phosphorus series non-halogen type XPM-1000 selected by fire retardant.

The complete water base organic foam material of polyurethane the most according to claim 7, it is characterised in that: described catalyst is selected and is contained There is the liquid catalyst of triethylene diamine.

9. the preparation method of the complete water base organic foam material of polyurethane as claimed in claim 1, comprises the steps:

1. amino resins, polyester polytrimethylene ether, high activity cross-linking agent, silicone oil are added in reactor, be heated to being warming up to 80 DEG C；

2. aforesaid reaction vessel being carried out evacuation, in question response still, vacuum reaches 0.8MP, reactor temperature rise to 100～ 105℃；

3., when reactor temperature drops to 80 DEG C naturally, nitrogen phosphorus series non-halogen type fire retardant is added；

4., when reactor temperature drops to 60 DEG C naturally, catalyst is added；

5., when reactor temperature drops to less than 50 DEG C naturally, after adding water and stirring 0.5h, it is cooled to room temperature；

6. the raw material in reactor and isocyanates are added in injection machine, foamable reaction in the mould of injection machine, hardening Rear material molding.