CN107793548A - A kind of dual-component polyurethane resin, its preparation method and use it for the technique for preparing polyurethane pultrusion composite materials - Google Patents
A kind of dual-component polyurethane resin, its preparation method and use it for the technique for preparing polyurethane pultrusion composite materials Download PDFInfo
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- CN107793548A CN107793548A CN201711043888.7A CN201711043888A CN107793548A CN 107793548 A CN107793548 A CN 107793548A CN 201711043888 A CN201711043888 A CN 201711043888A CN 107793548 A CN107793548 A CN 107793548A
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group 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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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- C08G18/40—High-molecular-weight compounds
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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Abstract
The present invention provides a kind of dual-component polyurethane resin a kind of dual-component polyurethane resin, its preparation method and the technique for using it for preparing polyurethane pultrusion composite materials, dual-component polyurethane resin provided by the invention, and its raw material includes the raw material of following parts by weight：150 ~ 200 parts of isocyanates, 120 ~ 170 parts of polymer polyatomic alcohol, 8 ~ 15 parts of chain extender, 2 ~ 5 parts of inner pattern releasing agent applicable, 0.1 ~ 0.5 part of catalyst, 0.1 ~ 0.6 part of defoamer, deicer 0.1 ~ 0.5, by polymer polyatomic alcohol, vacuum dehydration is carried out under the conditions of 110 ~ 120 DEG C carry out vacuum dehydration in 1.5 ~ 5 hours after chain extender mixing, inner pattern releasing agent applicable is added after cooling, catalyst, defoamer, deicer, it is well mixed to obtain B material, it is well mixed to obtain dual-component polyurethane resin using as the isocyanates that A expects with B material using static mixer, the polyurethane pultrusion composite materials that dual-component polyurethane resin provided by the invention is prepared have hardness height, the advantages of intensity is high.
Description
Technical field
The invention belongs to chemical industry composite synthesis technical field, and in particular to a kind of dual-component polyurethane resin, its system
Preparation Method and use it for the technique for preparing polyurethane pultrusion composite materials.
Background technology
Pultrusion composite materials are obtained by different matrix resin and reinforcing material are compound after certain design, traditional drawing
Crowded composite matrix resin is generally unsaturated polyester (UP), epoxy resin and vinylite etc..Unsaturated polyester (UP) mechanical performance
It is poor, it is not corrosion-resistant, and contain styrene, environmental pollution is larger.Epoxy resin price is higher, is of limited application；Together
When viscosity it is larger, be unfavorable for the complete wetting of fiber；Curing rate is slow, low production efficiency；And the too high degree of cross linking is easily caused
Product embrittlement；Vinylite alkali resistance is poor, while not impact resistance.
Polyurethane pultrusion composite materials have that mechanical performance is high, corrosion-resistant, ageing-resistant, production efficiency is high, is waved without styrene
Many advantages, such as hair, therefore the polyurethane pultrusion composite materials that a kind of hardness of offer is high, intensity is high have very big economic value.
The content of the invention
Based on above prior art, it is an object of the invention to provide a kind of dual-component polyurethane resin, its preparation method
And use it for preparing the technique of polyurethane pultrusion composite materials, it is standby using dual-component polyurethane resin-made provided by the invention
Obtained polyurethane pultrusion composite materials have the advantages of hardness is high, intensity is high.
In order to realize the above object the technical solution adopted by the present invention is：A kind of dual-component polyurethane resin, including it is following
The raw material of parts by weight：
Preferably, the isocyanates is MDI-50, MDI-100, liquefied mdi, at least one in modified MDI, PAPI
Kind, wherein, preferably its NCO content be 28-32%, average functionality 2-3%, in addition, modified MDI is preferably modified using urethane
NCO group content is high in MDI and/or Carbodiimide-Modified MDI, MDI type isocyanates, and reactivity is high, can be with polyalcohol
Rapid polymerization, it is especially suitable for fast pultrusion technique.
Preferably, the polymer polyatomic alcohol is PPG and/or PEPA, wherein, PPG
Initiator be preferably adopted as ethylene glycol, propane diols, glycerine, Glycerin, pentaerythrite, xylitol, sorbierite and sugarcane
At least one of sugar, the molecular weight of PPG is preferably 20~4500；PEPA is preferably more using normal polyester
The molecular weight of at least one of first alcohol, polycaprolactone polyol and PCDL, preferably PEPA is 500-
2000；.
Preferably, the chain extender be ethylene glycol, Isosorbide-5-Nitrae butanediol, 1,6 hexylene glycols, diglycol, HQEE-L,
At least one of small molecular alcohols such as MOCA, DMTDA, DETDA, from small molecular alcohol as chain extender, polyurethane can be improved
The intensity and hardness of pultrusion composite materials product.
The inner pattern releasing agent applicable is the mixed solution containing organic aliphatic acid and amine, it is ensured that pultrusion linear velocity reaches most
It hurry up, while the wellability of reinforcing material can be improved, reduce the abrasion of composite and die surface.
Preferably, the catalyst is tertiary amine catalyst and/or Organometal compound catalyst, wherein, tertiary amine is urged
Agent can include triethylenediamine, at least one of double (dimethylaminoethyl) ethers, cyclohexyl methyl tertiary amine, organic
The preferred organic heavy metal catalyst of metal compound as catalyst, can be that organotin catalysts, organozinc catalyst, organo-bismuth are urged
Agent, bismuth-zinc are at least one of catalyst compounded, and catalyst hardly plays catalysis to polyurethane resin reaction at normal temperatures and made
With, but the reaction speed of polyurethane resin can be accelerated at 100 DEG C, it can so ensure to use polyurethane resin system under normal temperature
Possess longer working life during standby polyurethane pultrusion composite materials, there is faster curing molding speed during high temperature.
Preferably, the defoamer is at least one in organic silicon defoamer, polymer defoamer, Organic fluoride defoamer
Kind, wherein, organosilicon and polymer defoamer, can making the minute bubbles in system, aggregation forms air pocket rapidly, makees in buoyancy
Surface is climbed under, is then ruptured.Meanwhile organosilicon, polymer defoamer also have prevent product surface defect
Function.
Preferably, the deicer be molecular sieve desiccant, oxazolidines deicer, in carbodiimides deicer extremely
Few one kind, wherein, Carbodiimides deicer is preferredPolycarbodiimide, N, N`- dicyclohexyl carbodiimides, 1,3-
At least one of dicyclohexyl carbodiimide.
The present invention also provides one kind and prepares dual-component polyurethane resin and use it for preparing polyurethane pultrusion composite materials
Technique, comprise the following steps：
Step 1, according to the parts by weight each raw material is weighed, it is standby；
Step 2, vacuum dehydration 1.5~5 hours is carried out under the conditions of 110~120 DEG C after mixing polymer polyatomic alcohol, chain extender
Vacuum dehydration is carried out, inner pattern releasing agent applicable, catalyst, defoamer, deicer are added after cooling, is entered with 120~400r/min speed
Row stirring obtains B material in 30~400 minutes to each component is well mixed, using static mixer using the isocyanates expected as A with
B material are well mixed, obtain dual-component polyurethane resin；
Step 3, reinforcing material to be composite is immersed in the dual-component polyurethane resin that step 2 obtains and answered with being infiltrated
Close and just expect, infiltrating time is 0.5~3 minute, afterwards by compound just material with 1~5cm/s speed by with three sections of warm areas
For mould to be solidified, it is that 140 DEG C of gel areas, temperature are that three sections of warm areas, which are followed successively by the preheating zone, temperature that temperature is 100 DEG C,
150 DEG C of curing areas, compound just material enter from preheating zone, from curing area export to obtain polyurethane pultrusion behind gel area compound
Material, compound just to expect after entering mould preheating zone, the temperature of dual-component polyurethane resin is gradually risen, and viscosity is gradually reduced, and is made
Further infiltration is in dual-component polyurethane resin for reinforcing material, and during by gel area, dual-component polyurethane resin is heated to be occurred
Cross-linking reaction, be gradually hardened, start that there is certain intensity, into curing area after continue to solidify, and ensure to reach one during depanning
Fixed curing degree.
Preferably, reinforcing material to be composite in the step 3 is glass fibre or carbon fiber.
Preferably, in the step 3 in obtained polyurethane pultrusion composite materials reinforcing material content for 80% with
On.
Beneficial effect
Beneficial effects of the present invention are as follows：
(1) traditional polyurethane resin crosslink density is typically lower than unsaturated polyester resin and vinylite, therefore matrix tree
The mechanical property of fat is also below unsaturated polyester resin and vinylite, but the present invention is mainly using isocyanates and high function
Polymerisation occurs for the polymer polyatomic alcohol of degree, and isocyanates and polymer polyatomic alcohol average functionality are high, is increasing chain link
The higher degree of cross linking can be provided simultaneously, highdensity cross-linked network can be formed, ensure that the mechanical property of material, is added simultaneously
The chain extender of the relative small molecule entered further increases the intensity and hardness of polyurethane resin.The dual-component polyurethane of the present invention
Resin can keep longer working life, when the temperature increases, also can reach rapid polymerization effect, be especially suitable for fast pultrusion work
Skill.
(2), the content of reinforcing material is high in polyurethane pultrusion composite materials, therefore is made from the isocyanates compared with low viscosity
For one of raw material, the reinforcing material to ensure as reinforcing material can fully be soaked by the polyurethane resin as matrix resin
Profit, wherein viscosity of the isocyanates as A material under the conditions of 25 DEG C is 50~300mPas, B expects the viscosity under the conditions of 25 DEG C
For 500~950mPas, initial mixing of the obtained dual-component polyurethane resin under the conditions of 25 DEG C after being mixed using A material with B material
Viscosity is 200~500mPas, so as to reach optimal effect of impregnation.
Embodiment
The present invention is described in further detail with reference to specific embodiment.
Embodiment 1
The present embodiment provides a kind of dual-component polyurethane resin, includes the raw material of following parts by weight：
Wherein, the isocyanates is 60 parts of Carbodiimide-Modified MDI and 130 parts of PAPI, and the polymer polyatomic alcohol is 100
Three official's PPGs that part molecular weight is 450, four official's PPGs that 50 parts of molecular weight are 700, the chain extender is second
Glycol, the catalyst are cyclohexyl methyl tertiary amine, and the defoamer is Organic fluoride defoamer.
The present invention also provides one kind and prepares dual-component polyurethane resin and use it for preparing polyurethane pultrusion composite materials
Technique, comprise the following steps：
Step 1, according to the parts by weight each raw material is weighed, it is standby；
Step 2, by polymer polyatomic alcohol, chain extender mix after at 115 DEG C vacuum dehydration 3~4 hours, after cooling add in take off
Mould agent, catalyst, defoamer, deicer, it is stirred 270 minutes with 180r/min speed and is obtained to each component is well mixed
B expects, is well mixed using static mixer using as the isocyanates that A expects with B material, obtains dual-component polyurethane resin；
Step 3, glass fibre to be composite is immersed in the dual-component polyurethane resin that step 2 obtains and answered with being infiltrated
Close and just expect, infiltrating time is 3 minutes, afterwards by compound just material with 2cm/s speed by the mould with three sections of warm areas to enter
Row solidification, three sections of warm areas be followed successively by the preheating zone, temperature that temperature is 100 DEG C be 140 DEG C of gel areas, temperature be 150 DEG C solid
Change area, compound just material enters from preheating zone, exports from curing area to obtain polyurethane pultrusion composite materials behind gel area, its
In, glass fibre accounts for the 81% of polyurethane pultrusion composite materials gross weight.
Embodiment 2
The present embodiment provides a kind of dual-component polyurethane resin, includes the raw material of following parts by weight：
Wherein, described 80 parts of MDI-50 and 90 part of Carbodiimide-Modified MDI, the polymer polyatomic alcohol are that 60 parts of molecular weight are
650 polytetrahydrofuran diol, 70 parts of molecular weight are 500, and degree of functionality is 3 ethylene oxide-capped PPG, described
Chain extender is DETDA, and the catalyst is that bismuth-zinc is catalyst compounded, and the defoamer is polymer defoamer.
The present invention also provides one kind and prepares dual-component polyurethane resin and use it for preparing polyurethane pultrusion composite materials
Technique, comprise the following steps：
Step 1, according to the parts by weight each raw material is weighed, it is standby；
Step 2, by polymer polyatomic alcohol, chain extender mix after at 110 DEG C vacuum dehydration 2~3 hours, after cooling add in take off
Mould agent, catalyst, defoamer, deicer, it is stirred 250 minutes with 250r/min speed and is obtained to each component is well mixed
B expects, is well mixed using static mixer using as the isocyanates that A expects with B material, obtains dual-component polyurethane resin；
Step 3, reinforcing material to be composite is immersed in the dual-component polyurethane resin that step 2 obtains and answered with being infiltrated
Close and just expect, infiltrating time is 2 minutes, afterwards by compound just material with 4cm/s speed by the mould with three sections of warm areas to enter
Row solidification, three sections of warm areas be followed successively by the preheating zone, temperature that temperature is 100 DEG C be 140 DEG C of gel areas, temperature be 150 DEG C solid
Change area, compound just material enters from preheating zone, exports from curing area to obtain polyurethane pultrusion composite materials behind gel area, its
In, glass fibre accounts for the 81% of polyurethane pultrusion composite materials gross weight.
Embodiment 3
The present embodiment provides a kind of dual-component polyurethane resin, includes the raw material of following parts by weight：
Wherein, the isocyanates is 70 parts of MDI-50 and 100 part of PAPI70, and the polymer polyatomic alcohol is that 60 parts of molecular weight are
2000 two official's PPGs, 80 parts of molecular weight are 600 four official's PPGs, and the chain extender is 1,6 hexylene glycols, institute
It is organozinc catalyst to state catalyst, and the defoamer is machine silicon defoaming agent.
The present invention also provides one kind and prepares dual-component polyurethane resin and use it for preparing polyurethane pultrusion composite materials
Technique, comprise the following steps：
Step 1, according to the parts by weight each raw material is weighed, it is standby；
Step 2, by polymer polyatomic alcohol, chain extender mix after at 120 DEG C vacuum dehydration 2~3 hours, after cooling add in take off
Mould agent, catalyst, defoamer, deicer, it is stirred 300 minutes with 400r/min speed and is obtained to each component is well mixed
B expects, is well mixed using static mixer using as the isocyanates that A expects with B material, obtains dual-component polyurethane resin；
Step 3, reinforcing material to be composite is immersed in the dual-component polyurethane resin that step 2 obtains and answered with being infiltrated
Close and just expect, infiltrating time is 3 minutes, afterwards by compound just material with 3cm/s speed by the mould with three sections of warm areas to enter
Row solidification, three sections of warm areas be followed successively by the preheating zone, temperature that temperature is 100 DEG C be 140 DEG C of gel areas, temperature be 150 DEG C solid
Change area, compound just material enters from preheating zone, exports from curing area to obtain polyurethane pultrusion composite materials behind gel area, its
In, glass fibre accounts for the 81% of polyurethane pultrusion composite materials gross weight.
Raw material is as shown in table 1 below used by dual-component polyurethane resin is prepared in above-described embodiment 1 to 3：
Table 1
| Raw material | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Isocyanates | 190 parts | 170 | 170 |
| Polymer polyatomic alcohol | 150 | 130 | 140 |
| Chain extender | 10 | 15 | 8 |
| Inner pattern releasing agent applicable | 2 | 4 | 5 |
| Catalyst | 0.3 | 0.1 | 0.5 |
| Defoamer | 0.6 | 0.5 | 0.3 |
| Deicer | 0.3 | 0.2 | 0.2 |
Polyurethane pultrusion composite materials are made using the formula in above-described embodiment 1 to 3 and technique, itself and the city as reference examples
Common pultrusion composite materials properties are as shown in table 2 below on face：
Table 2
| Performance | Embodiment 1 | Embodiment 2 | Embodiment 3 | Reference examples |
| Hardness Barcol (Hba) | 75 | 72 | 69 | 70 |
| Longitudinal tensile strength (MPa) | 1066 | 1012 | 984 | 355 |
| Transverse tensile strength (MPa) | 53 | 55 | 51 | 22 |
| Buckling strength (MPa) | 1126 | 1087 | 1010 | 426 |
| Transverse bending strength (MPa) | 116 | 112 | 108 | 30 |
The polyurethane pultrusion composite materials obtained in above-described embodiment 1 to 3, its hardness is with intensity all higher than existing common on the market
Pultrusion composite materials, wherein, the properties of the polyurethane pultrusion composite materials obtained with embodiment 1 are optimal, to be optimal real
Apply example.
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention,
Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still may be used
To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic.
Within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., it should be included in the present invention's
Within protection domain.
Claims (10)
1. a kind of dual-component polyurethane resin, it is characterised in that include the raw material of following parts by weight：
Ingredients weight parts；
Isocyanates 150 ~ 200；
Polymer polyatomic alcohol 120 ~ 170；
Chain extender 8 ~ 15；
2 ~ 5 parts of inner pattern releasing agent applicable；
Catalyst 0.1 ~ 0.5；
Defoamer 0.1 ~ 0.6；
Deicer 0.1 ~ 0.5.
2. dual-component polyurethane resin according to claim 1, it is characterised in that the isocyanates be MDI-50,
At least one of MDI-100, liquefied mdi, modified MDI, PAPI.
3. dual-component polyurethane resin according to claim 1, it is characterised in that the polymer polyatomic alcohol is that polyethers is more
First alcohol and/or PEPA.
4. dual-component polyurethane resin according to claim 1, it is characterised in that the chain extender is ethylene glycol, Isosorbide-5-Nitrae fourth
Glycol, 1, at least one of 6 hexylene glycols, diglycol, HQEE-L, MOCA, DMTDA, DETDA.
5. dual-component polyurethane resin according to claim 1, it is characterised in that the catalyst is tertiary amine catalyst
And/or Organometal compound catalyst.
6. dual-component polyurethane resin according to claim 1, it is characterised in that the defoamer defoams for organosilicon
At least one of agent, polymer defoamer, Organic fluoride defoamer.
7. dual-component polyurethane resin according to claim 1, it is characterised in that the deicer is molecular sieve drying
At least one of Ji, oxazolidines deicer, carbodiimides deicer.
8. a kind of dual-component polyurethane resin prepared described in claim 1 to 7 simultaneously is used it for preparing polyurethane pultrusion compound
The technique of material, it is characterised in that comprise the following steps：
Step 1, according to the parts by weight each raw material is weighed, it is standby；
Step 2, will polymer polyatomic alcohol, chain extender mix after under the conditions of 110 ~ 120 DEG C carry out vacuum dehydration enter within 1.5 ~ 5 hours
Row vacuum dehydration, inner pattern releasing agent applicable, catalyst, defoamer, deicer are added after cooling, carried out with 120 ~ 400r/min speed
Stirring obtains B material in 30 ~ 400 minutes to each component is well mixed, is expected the isocyanates expected as A and B using static mixer
It is well mixed, obtain dual-component polyurethane resin；
Step 3, base material to be composite is immersed in the dual-component polyurethane resin that step 2 obtains and answered with being infiltrated
Close and just expect, infiltrating time is 0.5 ~ 3 minute, and compound just material is passed through into the mould with three sections of warm areas with 1 ~ 5cm/s speed afterwards
For tool to be solidified, it is that 140 DEG C of gel areas, temperature are that three sections of warm areas, which are followed successively by the preheating zone, temperature that temperature is 100 DEG C,
150 DEG C of curing areas, compound just material enter from preheating zone, export from curing area to obtain polyurethane pultrusion composite wood behind gel area
Material.
9. the technique according to claim 8 for being used to dual-component polyurethane resin prepare polyurethane pultrusion composite materials,
Characterized in that, reinforcing material to be composite in the step 3 is glass fibre or carbon fiber.
10. the technique according to claim 8 for being used to dual-component polyurethane resin prepare polyurethane pultrusion composite materials,
Characterized in that, the content of reinforcing material is more than 80% in obtained polyurethane pultrusion composite materials in the step 3.
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