CN106832887A - A kind of repeatedly foaming TPU composites and preparation method thereof - Google Patents
A kind of repeatedly foaming TPU composites and preparation method thereof Download PDFInfo
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- CN106832887A CN106832887A CN201710093503.1A CN201710093503A CN106832887A CN 106832887 A CN106832887 A CN 106832887A CN 201710093503 A CN201710093503 A CN 201710093503A CN 106832887 A CN106832887 A CN 106832887A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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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
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- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
- C08J9/10—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 nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The present invention provides a kind of repeatedly foaming TPU composites and preparation method thereof, and the raw material of the foaming TPU composites includes following composition：5 10 weight portion composite foamable agents, 80 95 weight portion TPU particles, 13 parts by weight of flame retardant, 13 weight portion foam stabilisers and 25 weight portion antioxidant.The present invention has obtained multiple expanded material by adding composite foamable agent in TPU particles, the multiple foaming at 40 250 DEG C can be completed, its product surface can't see obvious hole, better appearance, and effect of damping, noise reduction can be played, and product has good mechanical performance, pliability is good, processing characteristics is good, can be prepared as foam films product, has a good application prospect.
Description
Technical field
The invention belongs to technical field of polymer materials, it is related to a kind of foaming TPU composites and preparation method thereof, especially relates to
And a kind of repeatedly foaming TPU composites and preparation method thereof.
Background technology
Expanded material refer to can material interior evaporation produce bubble make porous mass foaming material, can be with
For making foamed plastics, foam rubber, foamed product etc., these expanded materials have well using preceding in multiple fields
Scape.
CN103030841A discloses a kind of Novel foam material, and it is equipped with auxiliary agent with pre-gelatinized cornstarch as base-material,
It is prepared from by conventional foam process.The expanded material, with pre-gelatinized cornstarch as base-material, the foaming of this pure bio-based
Material, can be degradable, does not produce destruction, nonpoisonous and tasteless, safety and environmental protection to environment.
CN104760179A discloses a kind of PU foaming bodies with second time of foaming function, and its raw material is：PU foaming raw materials
And the foaming agent of thermal expansion type, foaming agent was uniformly mixed into black material before foaming or white material is interior.Its addition is weight
Than 1-10%, PU foaming raw materials include polyurethane, polyalcohol, and polyurethane is black material, and polyalcohol is white material, the expanded material
Second time of foaming can be carried out, manufactured goods weight is low and intensity is high.
In order to meet demand of the more areas for expanded material especially multiple expanded material, expect that obtaining one kind can enter
The material that row repeatedly foams.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide one kind foaming TPU composites and its preparation side
Method, is especially to provide a kind of repeatedly foaming TPU composites and preparation method thereof.
It is that, up to this purpose, the present invention uses following technical scheme：
On the one hand, the present invention provides a kind of foaming TPU composites, and the raw material of the foaming TPU composites is included such as
Lower composition：
In the present invention system is combined using composite foamable agent with TPU particles and fire retardant, foam stabiliser and antioxidant
Standby to obtain the TPU composites that foam, resulting material can repeatedly be foamed, and its product surface can't see hole, relatively more beautiful
See, and effect of damping, noise reduction can be played.
In the present invention, the consumption of the composite foamable agent can be 5 weight portions, 5.5 weight portions, 6 weight portions, 6.5 weights
Amount part, 7 weight portions, 7.5 weight portions, 8 weight portions, 8.5 weight portions, 9 weight portions, 9.5 weight portions or 10 weight portions, its consumption mistake
I haven't seen you for ages causes that foaming effect is deteriorated, and consumption is crossed and can at most cause the larger hole of product surface producing ratio, is caused unsightly.
In the present invention, the consumption of the TPU particles can be 80 weight portions, 82 weight portions, 84 weight portions, 86 weight
Part, 88 weight portions, 90 weight portions, 92 weight portions, 94 weight portions or 95 weight portions.
In the present invention, the consumption of the fire retardant can be 1.3 weight portions, 1.5 weight portions, 1.8 weight portions, 2 weight
Part, 2.3 weight portions, 2.5 weight portions or 2.8 weight portions.
Preferably, the fire retardant is any one in antimony oxide, aluminium hydroxide, magnesium hydroxide or APP
Or at least two combination.
In the present invention, the consumption of the foam stabiliser can be 1.3 weight portions, 1.5 weight portions, 1.8 weight portions, 2
Weight portion, 2.3 weight portions, 2.5 weight portions or 2.8 weight portions.
In the present invention, the consumption of the antioxidant can be 2.3 weight portions, 2.5 weight portions, 2.8 weight portions, 3 weight
Part, 3.3 weight portions, 3.5 weight portions, 3.8 weight portions, 4 weight portions, 4.3 weight portions, 4.5 weight portions or 4.8 weight portions.
Preferably, the composite foamable agent includes the component of following mass percent：
In the present invention, the composite foamable agent can be realized being foamed under condition of different temperatures, by setting not
Same blowing temperature realizes the multiple foaming of material.
In the present invention, in the composite foamable agent expandable polystyrene (EPS) content can for 40%, 41%, 42%,
43%th, 44%, 45%, 46%, 47%, 48%, 49% or 50%.
In the present invention, in the composite foamable agent EVA resin content can for 20%, 21%, 22%, 23%,
24%th, 25%, 26%, 27%, 28%, 29% or 30%.
Preferably, in the EVA resin ethylene contents be 18-25%, such as 18%, 19%, 20%, 21%, 22%,
23%th, 24% or 25%.
In the present invention, in the composite foamable agent dimethyl ether consumption can for 5%, 6%, 7%, 8%, 9% or
10%.The blowing temperature of dimethyl ether is relatively low, can at a lower temperature realize foaming.
In the present invention, in the composite foamable agent blowing agent AC -3000H content can for 10%, 11%, 12%,
13%th, 14%, 15%, 16%, 17%, 18%, 19% or 20%.
In the present invention, in the composite foamable agent foaming agent AD-300 content can for 5%, 5.5%, 6%,
6.5%th, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% or 10%.
Preferably, the raw material of the TPU particles includes following component：
Prepared by adding Graphene, polystyrene, butadiene-styrene rubber in the raw material of TPU particles in the present invention
Obtain TPU particles, polystyrene, the intensity and toughness of the addition enhancing TPU materials of butadiene-styrene rubber.
In the present invention, the consumption of the diisocyanate can be 50 weight portions, 51 weight portions, 52 weight portions, 53 weights
Amount part, 54 weight portions, 55 weight portions, 56 weight portions, 57 weight portions, 58 weight portions, 59 weight portions or 60 weight portions.
In the present invention, the consumption of the polyalcohol can for 35 weight portions, 37 weight portions, 39 weight portions, 40 weight portions,
43 weight portions, 45 weight portions, 48 weight portions or 50 weight portions.
In the present invention, the consumption of the Graphene can for 1 weight portion, 1.5 weight portions, 2 weight portions, 2.5 weight portions,
3 weight portions, 3.5 weight portions, 4 weight portions, 4.5 weight portions or 5 weight portions.Graphene can be with the damping of reinforcing material, noise reduction work(
Effect.
In the present invention, the consumption of the polystyrene can be 6 weight portions, 7 weight portions, 8 weight portions, 9 weight portions, 10
Weight portion, 11 weight portions, 12 weight portions, 13 weight portions, 14 weight portions or 15 weight portions.
In the present invention, the consumption of the butadiene-styrene rubber can be 5 weight portions, 6 weight portions, 7 weight portions, 8 weight portions, 9
Weight portion or 10 weight portions.
In the present invention, the consumption of the chain extender can be 2 weight portions, 2.5 weight portions, 3 weight portions, 4 weight portions, 5
Weight portion, 6 weight portions, 7 weight portions or 8 weight portions.
In the present invention, the consumption of the catalyst can be 1.3 weight portions, 1.5 weight portions, 1.8 weight portions, 2 weight
Part, 2.3 weight portions, 2.5 weight portions or 2.8 weight portions.
Preferably, the raw material of the TPU particles includes following component：
Preferably, the diisocyanate is the mixture of toluene di-isocyanate(TDI) and hexamethylene diisocyanate, described polynary
Alcohol is PEPA and PPG.
Two kinds of specific diisocyanate, both diisocyanate and two kinds of polyalcohol phase interworkings are selected in the present invention
Close, be easier to control the soft section and hard section ratio of polyurethane than a kind of diisocyanate or a kind of polyalcohol is used alone, the two
Mechanical property, elasticity and flexibility in enhancing polyurethane have synergy.
Preferably, the mass ratio of the toluene di-isocyanate(TDI) and hexamethylene diisocyanate is (2-5):1, such as 2:1、.3:
1、4:1 or 5:1, two kinds of specific diisocyanate are used in conjunction with each other, and can preferably adjust the wearability of polyurethane material
And pliability.
Preferably, the mass ratio of PEPA and PPG is (1-4) in the polyalcohol:1, such as 1:1、
1.5:1、2:1、2.5:1、3:1、3.5:1 or 4:1.
Preferably, the weight average molecular weight of the polyalcohol be 500-3500, such as 500,1000,1500,2000,3000 or
3500, preferably 1000-2000.
Preferably, the weight average molecular weight of the polystyrene be 5000-10000, such as 5000,6000,7000,8000,
9000 or 10000.
Preferably, the chain extender is in ethylene glycol, ethylenediamine, 1,3-PD, BDO or 1,5-PD
Any one or at least two combination.
Preferably, the catalyst is any in stannous octoate, two sad dibutyl tins or dibutyl tin laurate
It is a kind of or at least two combination.
On the other hand, the invention provides the preparation method of foaming TPU composites as described above, methods described includes
Following steps：
(1) expandable polystyrene (EPS), EVA resin, dimethyl ether, blowing agent AC -3000H, foaming agent AD-300 are mixed equal
It is even, obtain composite foamable agent；
(2) diisocyanate is added in A storage tanks, polyalcohol is added in B storage tanks, chain extender and catalyst add
Enter in C storage tanks, under agitation, vacuum dehydration；
(3) by the raw material pumping in step (2) to double screw extruder, while adding Graphene, polystyrene, butylbenzene
Rubber, using double screw extruder reaction, granulation, obtains the TPU particles；
(4) TPU particles and fire retardant, foam stabiliser that the composite foamable agent that obtains step (1), step (3) are obtained
And antioxidant is well mixed, it is cast using single screw extrusion machine, obtains described foaming TPU composites.
Preferably, temperature during step (2) described vacuum dehydration be 60-80 DEG C, such as 60 DEG C, 63 DEG C, 65 DEG C, 68 DEG C,
70 DEG C, 72 DEG C, 75 DEG C, 78 DEG C or 80 DEG C.
Preferably, the speed of step (2) described stirring be 300-1000r/min, such as 300r/min, 400r/min,
500r/min, 600r/min, 800r/min or 1000r/min.
Preferably, pressure during step (2) described vacuum dehydration be -0.3~-0.1kPa, such as -0.3kPa, -
0.28kPa, -0.25kPa, -0.23kPa, -0.2kPa, -0.18kPa, -0.15kPa, -0.13kPa or -0.1kPa.
Preferably, the feeding section temperature of step (3) described double screw extruder is 110-120 DEG C, such as 112 DEG C, 115
DEG C, 118 DEG C or 120 DEG C, mixing section temperature be 130-150 DEG C, such as 132 DEG C, 135 DEG C, 138 DEG C, 140 DEG C, 143 DEG C, 145 DEG C
Or 148 DEG C, extruding zone temperature is 170-180 DEG C, such as 172 DEG C, 175 DEG C, 178 DEG C or 180 DEG C, and head temperature is 150-160
DEG C, such as 153 DEG C, 155 DEG C, 158 DEG C or 160 DEG C.
The foaming TPU composites that the present invention is prepared can repeatedly be foamed, and it can be in 40-250 DEG C of foaming
Repeatedly foaming is completed in temperature range；Can carry out first time foaming at 40-60 DEG C, foamed time be 10s-30s (such as 10s,
13s, 15s, 18s, 20s, 23s, 25s, 28s or 30s), now made mainly due to the volatilization of the dimethyl ether in composite foamable agent
Into foaming materials, second time of foaming can be carried out at 90-140 DEG C, now a part of expandable polystyrene (EPS) and foaming agent AD-300
Etc. can produce foaming, foamed time be 5-20min (such as 5min, 8min, 10min, 13min, 15min, 18min or
20min)；Three foaming can be carried out for 150-200 DEG C in temperature, now blowing agent AC -3000H and can in composite foamable agent
Expanded polystyrene (EPS) and TPU particles etc. can cause foaming, foamed time be 10-30min (such as 10min, 13min, 15min,
18min, 20min, 23min, 25min or 28min), the 4th foaming can be carried out at 220-250 DEG C, now composite foamable agent
Middle blowing agent AC -3000H and EVA resin and TPU particles can cause foaming, foamed time be 1-8min (such as 2min,
3min, 4min, 5min, 6min, 7min or 8min).
Mould of different shapes such as hemispherical can be used during material of the invention is foamed, is sent out
Bubble, so as to obtain product of different shapes.
In the present invention, the proportion after the foaming TPU composite one step foamings is 40-200 g/l, one step foaming times
Rate is 60-95% (such as 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%)；Second time of foaming multiplying power is 5-
40% (such as 5%, 8%, 10%, 15%, 18%, 20%, 25%, 30%, 35% or 40%), preferably 7-27%, three hairs
Bubble rate is 10-20% (such as 10%, 13%, 15%, 18% or 20%), four expansion ratios be 5-15% (such as 5%,
7%th, 9%, 11%, 13% or 15%).
On the other hand, the present invention provides a kind of foam films, and the foam films are by the TPU composite shapes that foam as described above
Into.
Foam films of the invention can be used for preparing has sandwich construction and with the product of secondary or multiple foam performance.
Relative to prior art, the invention has the advantages that：
The present invention has obtained multiple expanded material by adding composite foamable agent in TPU particles, can complete in 40-
Multiple foaming at 250 DEG C, its product surface can't see obvious hole, better appearance, and can play the work(of damping, noise reduction
Effect, and product has good mechanical performance, and pliability is good, and processing characteristics is good, can be prepared as foam films product, has
There is good application prospect.
Specific embodiment
Technical scheme is further illustrated below by specific embodiment.Those skilled in the art should be bright
, the embodiment be only to aid in understand the present invention, be not construed as to concrete restriction of the invention.
Embodiment 1
In the present embodiment, foaming TPU composites are prepared by following material composition：
The composite foamable agent includes the component of following mass percent：
The raw material of the TPU particles includes following component：
Wherein diisocyanate is the mixture of toluene di-isocyanate(TDI) and hexamethylene diisocyanate, toluene di-isocyanate(TDI) and
The mass ratio of hexamethylene diisocyanate is 3:1, the polyalcohol be PEPA and PPG, wherein PEPA and
The mass ratio of PPG is 2:1, the weight average molecular weight of the polyalcohol is 1500, the weight average molecular weight of the polystyrene
It is 5000, chain extender is ethylene glycol, catalyst is stannous octoate.
The preparation method of the foaming TPU composites is as follows：
(1) expandable polystyrene (EPS), EVA resin, dimethyl ether, blowing agent AC -3000H, foaming agent AD-300 are mixed equal
It is even, obtain composite foamable agent；
(2) diisocyanate is added in A storage tanks, polyalcohol is added in B storage tanks, chain extender and catalyst add
Enter in C storage tanks, 500r/min rotating speeds stirring under, under -0.3kPa pressure in 70 DEG C of vacuum dehydrations；
(3) by the raw material pumping in step (2) to double screw extruder, while adding Graphene, polystyrene, butylbenzene
Rubber, using double screw extruder reaction, granulation, obtains the TPU particles, and the feeding section temperature of double screw extruder is 110
DEG C, mixing section temperature is 130 DEG C, and it is 170 DEG C to go out section temperature, and head temperature is 150 DEG C；
(4) TPU particles and fire retardant, foam stabiliser that the composite foamable agent that obtains step (1), step (3) are obtained
And antioxidant is well mixed, it is cast using single screw extrusion machine, obtains described foaming TPU composites, single screw rod temperature
It it is 210 DEG C, die head temperature is 200 DEG C.
Embodiment 2
In the present embodiment, foaming TPU composites are prepared by following material composition：
The composite foamable agent includes the component of following mass percent：
The raw material of the TPU particles includes following component：
Wherein diisocyanate is the mixture of toluene di-isocyanate(TDI) and hexamethylene diisocyanate, toluene di-isocyanate(TDI) and
The mass ratio of hexamethylene diisocyanate is 4:1, the polyalcohol be PEPA and PPG, wherein PEPA and
The mass ratio of PPG is 3:1, the number-average molecular weight of the polyalcohol is 1000, the weight average molecular weight of the polystyrene
It is 10000, chain extender is ethylenediamine, catalyst is the fourth tin of moon silicic acid two.
The preparation method of the foaming TPU composites is as follows：
(1) expandable polystyrene (EPS), EVA resin, dimethyl ether, blowing agent AC -3000H, foaming agent AD-300 are mixed equal
It is even, obtain composite foamable agent；
(2) diisocyanate is added in A storage tanks, polyalcohol is added in B storage tanks, chain extender and catalyst add
Enter in C storage tanks, 600r/min rotating speeds stirring under, under -0.2kPa pressure in 80 DEG C of vacuum dehydrations；
(3) by the raw material pumping in step (2) to double screw extruder, while adding Graphene, polystyrene, butylbenzene
Rubber, using double screw extruder reaction, granulation, obtains the TPU particles, and the feeding section temperature of double screw extruder is 120
DEG C, mixing section temperature is 150 DEG C, and it is 180 DEG C to go out section temperature, and head temperature is 160 DEG C；
(4) TPU particles and fire retardant, foam stabiliser that the composite foamable agent that obtains step (1), step (3) are obtained
And antioxidant is well mixed, it is cast using single screw extrusion machine, obtains described foaming TPU composites, single screw rod temperature
It it is 208 DEG C, die head temperature is 198 DEG C.
Embodiment 3
In the present embodiment, foaming TPU composites are prepared by following material composition：
The composite foamable agent includes the component of following mass percent：
The raw material of the TPU particles includes following component：
Wherein diisocyanate is the mixture of toluene di-isocyanate(TDI) and hexamethylene diisocyanate, toluene di-isocyanate(TDI) and
The mass ratio of hexamethylene diisocyanate is 5:1, the polyalcohol be PEPA and PPG, wherein PEPA and
The mass ratio of PPG is 4:The number-average molecular weight of polyalcohol described in 1 is 1500, the weight average molecular weight of the polystyrene
It is 5000, chain extender is BDO, catalyst is two sad two fourths tin.
The preparation method of the foaming TPU composites is as follows：
(1) expandable polystyrene (EPS), EVA resin, dimethyl ether, blowing agent AC -3000H, foaming agent AD-300 are mixed equal
It is even, obtain composite foamable agent；
(2) diisocyanate is added in A storage tanks, polyalcohol is added in B storage tanks, chain extender and catalyst add
Enter in C storage tanks, 500r/min rotating speeds stirring under, under -0.1kPa pressure in 70 DEG C of vacuum dehydrations；
(3) by the raw material pumping in step (2) to double screw extruder, while adding Graphene, polystyrene, butylbenzene
Rubber, using double screw extruder reaction, granulation, obtains the TPU particles, and the feeding section temperature of double screw extruder is 120
DEG C, mixing section temperature is 140 DEG C, and it is 175 DEG C to go out section temperature, and head temperature is 155 DEG C；
(4) TPU particles and fire retardant, foam stabiliser that the composite foamable agent that obtains step (1), step (3) are obtained
And antioxidant is well mixed, it is cast using single screw extrusion machine, obtains described foaming TPU composites, single screw rod temperature
It it is 205 DEG C, die head temperature is 195 DEG C.
Embodiment 4
In the present embodiment, foaming TPU composites are prepared by following material composition：
The composite foamable agent includes the component of following mass percent：
The raw material of the TPU particles includes following component：
Wherein diisocyanate is the mixture of toluene di-isocyanate(TDI) and hexamethylene diisocyanate, toluene di-isocyanate(TDI) and
The mass ratio of hexamethylene diisocyanate is 2:1, the polyalcohol be PEPA and PPG, wherein PEPA and
The mass ratio of PPG is 1:The number-average molecular weight of polyalcohol described in 1 is 1500, the weight average molecular weight of the polystyrene
It is 5000, chain extender is BDO, catalyst is stannous octoate.
The preparation method of the foaming TPU composites is as follows：
(1) expandable polystyrene (EPS), EVA resin, dimethyl ether, blowing agent AC -3000H, foaming agent AD-300 are mixed equal
It is even, obtain composite foamable agent；
(2) diisocyanate is added in A storage tanks, polyalcohol is added in B storage tanks, chain extender and catalyst add
Enter in C storage tanks, 600r/min rotating speeds stirring under, under -0.3kPa pressure in 70 DEG C of vacuum dehydrations；
(3) by the raw material pumping in step (2) to double screw extruder, while adding Graphene, polystyrene, butylbenzene
Rubber, using double screw extruder reaction, granulation, obtains the TPU particles, and the feeding section temperature of double screw extruder is 110
DEG C, mixing section temperature is 130 DEG C, and it is 170 DEG C to go out section temperature, and head temperature is 150 DEG C；
(4) TPU particles and fire retardant, foam stabiliser that the composite foamable agent that obtains step (1), step (3) are obtained
And antioxidant is well mixed, it is cast using single screw extrusion machine, obtains described foaming TPU composites, single screw rod temperature
It it is 205 DEG C, die head temperature is 195 DEG C.
Comparative example 1
The comparative example be the difference is that only with embodiment 1, and composite foamable agent is not used in foaming TPU composites,
Remaining raw material is same as Example 1 with raw material dosage and preparation method.
Comparative example 2
The comparative example the difference is that only that the consumption of composite foamable agent is in foaming TPU composites with embodiment 1
3 weight portions, remaining raw material is same as Example 1 with raw material dosage and preparation method.
Comparative example 3
The comparative example the difference is that only that the consumption of composite foamable agent is in foaming TPU composites with embodiment 1
12 weight portions, remaining raw material is same as Example 1 with raw material dosage and preparation method.
Comparative example 4
The comparative example be the difference is that only with embodiment 1, and polystyrene and butylbenzene are added without in the raw material of TPU particles
Rubber, remaining raw material is same as Example 1 with raw material dosage and preparation method.
Comparative example 5
The comparative example the difference is that only that diisocyanate is single toluene di-isocyanate(TDI) with embodiment 1, its
Remaining raw material and raw material dosage and preparation method and condition are same as Example 1.
Comparative example 6
The comparative example the difference is that only that diisocyanate is single hexamethylene diisocyanate with embodiment 1, remaining
Raw material and raw material dosage and preparation method and condition are same as Example 1.
Comparative example 7
The comparative example the difference is that only with embodiment 1, the quality of toluene di-isocyanate(TDI) and hexamethylene diisocyanate
Than being 1:2, remaining raw material and raw material dosage and preparation method and condition are same as Example 1.
Comparative example 8
The comparative example the difference is that only with embodiment 1, the quality of toluene di-isocyanate(TDI) and hexamethylene diisocyanate
Than being 1:1, remaining raw material and raw material dosage and preparation method and condition are same as Example 1.
Comparative example 9
The comparative example the difference is that only that the polyalcohol is single PPG with embodiment 1, and remaining is former
Material and raw material dosage and preparation method and condition are same as Example 1.
Comparative example 10
The comparative example the difference is that only that the polyalcohol is single PEPA with embodiment 1, and remaining is former
Material and raw material dosage and preparation method and condition are same as Example 1.
Comparative example 11
The comparative example the difference is that only that the mass ratio of PEPA and PPG is 1 with embodiment 1:
2, remaining raw material and raw material dosage and preparation method and condition are same as Example 1.
Comparative example 12
The comparative example the difference is that only that the mass ratio of PEPA and PPG is 6 with embodiment 1:
1, remaining raw material and raw material dosage and preparation method and condition are same as Example 1.
Comparative example 13
The comparative example the difference is that only that the weight average molecular weight of the polyalcohol is 400, and remaining is former with embodiment 1
Material and raw material dosage and preparation method and condition are same as Example 1.
Comparative example 14
The comparative example the difference is that only that the weight average molecular weight of the polyalcohol is 4000, and remaining is former with embodiment 1
Material and raw material dosage and preparation method and condition are same as Example 1.
The tensile strength of the TPU composites prepared to embodiment 1-5 and comparative example 1-14, elongation at break with
And foam performance is tested, its test result is as shown in table 1.
Table 1
It refers to that can carry out first time foaming at 40-60 DEG C to be capable of achieving four foaming at 40-250 DEG C described in table 1, during foaming
Between be 10s-30s；Second time of foaming can be carried out at 90-140 DEG C, foamed time is 5-20min, three can be carried out at 150-200 DEG C
Secondary foaming, foamed time is 10-30min；The 4th foaming can be carried out at 220-250 DEG C, foamed time is 1-8min.
As can be seen from Table 1, the present invention has obtained multiple foaming material by adding composite foamable agent in TPU particles
Material, can complete the multiple foaming at 40-250 DEG C, and its product surface can't see obvious hole, better appearance, and can be with
Effect of damping, noise reduction is played, and product has good mechanical performance, and pliability is good, and processing characteristics is good, can make
Standby is foam films product, is had a good application prospect.
Applicant state, the present invention illustrated by above-described embodiment multiple foaming TPU composites of the invention and its
Preparation method, but the invention is not limited in above-described embodiment, that is, do not mean that the present invention has to rely on above-described embodiment ability
Implement.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention, to each raw material of product of the present invention etc.
Effect replacement and addition, selection of concrete mode of auxiliary element etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (10)
1. a kind of foaming TPU composites, it is characterised in that the raw material of the foaming TPU composites includes following composition：
2. foaming TPU composites according to claim 1, it is characterised in that the composite foamable agent includes following matter
Measure the component of percentage：
3. foaming TPU composites according to claim 2, it is characterised in that ethylene contents are in the EVA resin
18-25%.
4. foaming TPU composites according to any one of claim 1-3, it is characterised in that the original of the TPU particles
Material includes following component：
5. foaming TPU composites according to claim 4, it is characterised in that the raw material of the TPU particles includes following
Composition：
Preferably, the diisocyanate is the mixture of toluene di-isocyanate(TDI) and hexamethylene diisocyanate, and the polyalcohol is
PEPA and PPG；
Preferably, the mass ratio of the toluene di-isocyanate(TDI) and hexamethylene diisocyanate is (2-5):1；
Preferably, the mass ratio of PEPA and PPG is (1-4) in the polyalcohol:1；
Preferably, the weight average molecular weight of the polyalcohol is 500-3500, preferably 1000-2000；
Preferably, the weight average molecular weight of the polystyrene is 5000-10000；
Preferably, the chain extender is appointing in ethylene glycol, ethylenediamine, 1,3-PD, BDO or 1,5-PD
Meaning it is a kind of or at least two combinations；
Preferably, the catalyst is any one in stannous octoate, two sad dibutyl tins or dibutyl tin laurate
Or at least two combination.
6. foaming TPU composites according to any one of claim 1-5, it is characterised in that the fire retardant is three
Aoxidize in two antimony, aluminium hydroxide, magnesium hydroxide or APP any one or at least two combination.
7. the preparation method of the foaming TPU composites according to any one of claim 1-6, it is characterised in that described
Method is comprised the following steps：
(1) expandable polystyrene (EPS), EVA resin, dimethyl ether, blowing agent AC -3000H, foaming agent AD-300 are well mixed, are obtained
To composite foamable agent；
(2) diisocyanate is added in A storage tanks, polyalcohol is added in B storage tanks, chain extender and catalyst are added to
In C storage tanks, under agitation, vacuum dehydration；
(3) by the raw material pumping in step (2) to double screw extruder, while adding Graphene, polystyrene, butylbenzene rubber
Glue, using double screw extruder reaction, granulation, obtains the TPU particles；
(4) TPU particles that the composite foamable agent that obtains step (1), step (3) are obtained and fire retardant, foam stabiliser and
Antioxidant is well mixed, and described foaming TPU composites are obtained using single screw extrusion machine curtain coating.
8. preparation method according to claim 7, it is characterised in that temperature during step (2) described vacuum dehydration is 60-
80℃；
Preferably, the speed of step (2) described stirring is 300-1000r/min；
Preferably, pressure during step (2) described vacuum dehydration is -0.3~-0.1kPa.
9. the preparation method according to claim 7 or 8, it is characterised in that the feeding of step (3) described double screw extruder
Duan Wendu is 110-120 DEG C, and mixing section temperature is 130-150 DEG C, and extruding zone temperature is 170-180 DEG C, and head temperature is 150-
160℃；The extruder temperature of the single screw extrusion machine described in step (4) is 190-220 DEG C, and die head temperature is 180-200 DEG C.
10. a kind of foam films, it is characterised in that the foam films are answered as the foaming TPU as any one of claim 1-6
Condensation material is formed.
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Application publication date: 20170613 |