CN117700663A - Spray-type polyurethane hard foam composition and application thereof - Google Patents
Spray-type polyurethane hard foam composition and application thereof Download PDFInfo
- Publication number
- CN117700663A CN117700663A CN202311620956.7A CN202311620956A CN117700663A CN 117700663 A CN117700663 A CN 117700663A CN 202311620956 A CN202311620956 A CN 202311620956A CN 117700663 A CN117700663 A CN 117700663A
- Authority
- CN
- China
- Prior art keywords
- oil polyol
- spray
- parts
- hard foam
- polyurethane hard
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000006260 foam Substances 0.000 title claims abstract description 69
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 53
- 239000004814 polyurethane Substances 0.000 title claims abstract description 53
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 81
- 229920005862 polyol Polymers 0.000 claims abstract description 54
- 150000003077 polyols Chemical class 0.000 claims abstract description 54
- 238000005507 spraying Methods 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 239000002608 ionic liquid Substances 0.000 claims abstract description 25
- 239000004088 foaming agent Substances 0.000 claims abstract description 23
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 22
- 239000008158 vegetable oil Substances 0.000 claims abstract description 22
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003063 flame retardant Substances 0.000 claims abstract description 21
- 239000003381 stabilizer Substances 0.000 claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims description 22
- 239000003549 soybean oil Substances 0.000 claims description 13
- 235000012424 soybean oil Nutrition 0.000 claims description 13
- 150000001768 cations Chemical class 0.000 claims description 12
- 150000001450 anions Chemical class 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- FYXPKOPFEGFWHG-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-phenylphosphoryl]phenol Chemical compound C1=CC(O)=CC=C1P(=O)(C=1C=CC(O)=CC=1)C1=CC=CC=C1 FYXPKOPFEGFWHG-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 239000003341 Bronsted base Substances 0.000 claims description 2
- CGSLYBDCEGBZCG-UHFFFAOYSA-N Octicizer Chemical compound C=1C=CC=CC=1OP(=O)(OCC(CC)CCCC)OC1=CC=CC=C1 CGSLYBDCEGBZCG-UHFFFAOYSA-N 0.000 claims description 2
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- 235000019483 Peanut oil Nutrition 0.000 claims description 2
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- 235000019486 Sunflower oil Nutrition 0.000 claims description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 2
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 claims description 2
- GTVWRXDRKAHEAD-UHFFFAOYSA-N Tris(2-ethylhexyl) phosphate Chemical compound CCCCC(CC)COP(=O)(OCC(CC)CCCC)OCC(CC)CCCC GTVWRXDRKAHEAD-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000005018 casein Substances 0.000 claims description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims description 2
- 235000021240 caseins Nutrition 0.000 claims description 2
- 239000003240 coconut oil Substances 0.000 claims description 2
- 235000019864 coconut oil Nutrition 0.000 claims description 2
- 239000002285 corn oil Substances 0.000 claims description 2
- 235000005687 corn oil Nutrition 0.000 claims description 2
- 235000012343 cottonseed oil Nutrition 0.000 claims description 2
- 239000002385 cottonseed oil Substances 0.000 claims description 2
- 239000012774 insulation material Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000004006 olive oil Substances 0.000 claims description 2
- 235000008390 olive oil Nutrition 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- 239000000312 peanut oil Substances 0.000 claims description 2
- 239000008159 sesame oil Substances 0.000 claims description 2
- 235000011803 sesame oil Nutrition 0.000 claims description 2
- 239000002600 sunflower oil Substances 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- JZZBTMVTLBHJHL-UHFFFAOYSA-N tris(2,3-dichloropropyl) phosphate Chemical compound ClCC(Cl)COP(=O)(OCC(Cl)CCl)OCC(Cl)CCl JZZBTMVTLBHJHL-UHFFFAOYSA-N 0.000 claims description 2
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 claims description 2
- 238000005187 foaming Methods 0.000 abstract description 12
- 238000007711 solidification Methods 0.000 abstract description 11
- 230000008023 solidification Effects 0.000 abstract description 11
- 238000010276 construction Methods 0.000 abstract description 8
- 238000004321 preservation Methods 0.000 abstract description 8
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- 238000009413 insulation Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 24
- 229920002545 silicone oil Polymers 0.000 description 13
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical group CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 239000007921 spray Substances 0.000 description 6
- 229920005830 Polyurethane Foam Polymers 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 239000011496 polyurethane foam Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 210000004177 elastic tissue Anatomy 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of chemical materials and production thereof, and particularly relates to a spray-type polyurethane hard foam composition and application thereof. The spray-type polyurethane hard foam composition consists of a material A and a material B, wherein the material A and the material B are respectively and independently packaged; the material A comprises the following components in parts by weight: 100 parts of vegetable oil polyol; 0.1-1 part of ionic liquid catalyst; 1-5 parts of foaming agent; 1-3 parts of foam stabilizer; 10-20 parts of flame retardant; the material B is polymeric MDI. The invention adopts vegetable oil polyol with specific hydroxyl value as raw material, and the prepared bio-based polyurethane hard foam has good adhesive property and mechanical property, and simultaneously has good heat preservation and water insulation effects. The novel compounding and catalyzing system is adopted, the prepared spraying type bio-based polyurethane hard foam has short reaction time, and the spraying type bio-based polyurethane hard foam can be obtained by solidification within 2 minutes after spraying and foaming, so that the requirements of site construction can be met.
Description
Technical Field
The invention belongs to the technical field of chemical materials and production thereof, and particularly relates to a spray-type polyurethane hard foam composition and application thereof.
Background
Polyurethane is a polymer having urethane segment repeating structural units made from the reaction of an isocyanate with a polyol. Polyurethane products are classified into two main categories, foamed products and non-foamed products. The foaming product is soft, hard and semi-hard polyurethane foam plastic; non-foamed articles include coatings, adhesives, synthetic leather, elastomers, elastic fibers, and the like. The polyurethane hard foam is an important functional material, and is widely applied to various industries such as building heat preservation, pipeline heat preservation, household appliance heat preservation, decoration, light plates, automobile manufacture, electronic element manufacture and the like because of good heat insulation performance, good adhesive force, high specific strength and excellent durability.
The heat preservation and water isolation requirements of the railway tunnel are extremely complex, and the heat preservation and water isolation requirements are significant for railway construction in China. For example, in a railway of 1100 km from Lhasa to Linzhi, the bridge-tunnel ratio is more than 80%, which is equivalent to digging a tunnel from Beijing to Nanjing, and digging and chiseling in mountain bodies, the temperature difference between the tunnel and the mountain bodies is large due to the pressure of the mountain bodies, which can reach 70 ℃ or higher, and the requirement on heat preservation is high; meanwhile, mountain water seepage is serious, and the mountain water seepage is alkaline, and has high requirements on water isolation and weather resistance; in addition, the construction environment has complex base materials and high requirement on the bonding strength of the hard foam; in addition, the vibration environment, long service life and the like of the tunnel require good shock resistance and stability of the material; meanwhile, the tunnel construction has remote geographical environment, inconvenient traffic, effective space in the tunnel, high requirements on material storage and transportation and construction convenience, and hopefully can be sprayed and formed on site.
Polyurethane prepared from traditional petrochemical polyol is low in adhesive force, is not suitable for a substrate environment with complex tunnels, and can form hollow grains to influence the heat insulation and water isolation performance of hard bubbles. While vegetable oil polyols can enhance product properties by introducing specific groups such as: through polyhydroxy introduction, a cross-linked structure is obtained, the stability and weather resistance of the material are improved, the closed porosity of the material is improved, and the water-proof and heat-insulating properties are optimized; the damping property of the material is improved through the suspension chain, and the earthquake resistance is optimized. However, the formulation and catalytic system of the spray polyurethane are developed for petrochemical polyols and are not suitable for vegetable oil polyols. Therefore, development of a compounding system suitable for the vegetable oil polyol is urgently required, the reaction is performed in a short time, and the requirements of site construction and the like are met.
Disclosure of Invention
The invention aims to solve the technical problem of providing a spray-type polyurethane hard foam and a preparation method and application thereof aiming at the defects of the prior art.
The invention is characterized in that: in order to ensure that the spray-type bio-based rigid foam can meet the heat-insulating and water-insulating requirements of a railway tunnel and has excellent mechanical properties, a formula suitable for vegetable oil polyol is developed, polyurethane can be foamed and hardened in a rapid reaction manner, the requirements of site construction are met, and meanwhile, the spray-type bio-based rigid foam has excellent heat-insulating and water-insulating properties and mechanical properties.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention discloses a spray-type polyurethane hard foam composition, which consists of a material A and a material B, wherein the material A and the material B are respectively and independently packaged;
the material A comprises the following components in parts by weight:
100 parts of vegetable oil polyol;
0.1-1 part of ionic liquid catalyst;
1-5 parts of foaming agent;
1-3 parts of foam stabilizer;
10-20 parts of flame retardant;
the material B is polymeric MDI;
preferably, the material A comprises the following components in parts by weight:
100 parts of vegetable oil polyol;
0.2 to 0.6 portion of ionic liquid catalyst;
3 parts of foaming agent;
2 parts of foam stabilizer;
15 parts of flame retardant;
the material B is polymeric MDI;
wherein the material A does not contain a cross-linking agent and water; the material B does not contain a cross-linking agent and water.
Among them, the crosslinking agent is commonly used in the technical field such as glycerin, trimethylolpropane, pentaerythritol, diethanolamine, etc.
In some embodiments, the vegetable oil polyol is any one or a combination of several of olive oil polyol, peanut oil polyol, rapeseed oil polyol, cottonseed oil polyol, soybean oil polyol, coconut oil polyol, palm oil polyol, sesame oil polyol, corn oil polyol, and sunflower oil polyol, preferably soybean oil polyol; the hydroxyl value of the vegetable oil polyol is 300-500 mg KOH/g.
Wherein the vegetable oil polyol is prepared according to the prior art (Chinese patent application No. 201310247746.8).
In some embodiments, the ionic liquid catalyst is a pyridine-type ionic liquid catalyst, an imidazole-type ionic liquid catalyst, or a long chain aliphatic amine-type ionic liquid catalyst; the anion of the ionic liquid catalyst is Bronsted alkali; the Bronsted base is dicyandiamide radical, hexafluorophosphate radical, boron tetrafluoride ion or bis-trifluoromethanesulfonyl imide radical, preferably dicyandiamide radical; the cation of the ionic liquid catalyst is preferably any one of cations shown in the following structures:
further preferred is
In some embodiments, the foaming agent is any one or a combination of two of a physical foaming agent and a chemical foaming agent; preferably, the foaming agent is a physical foaming agent; further preferably, the foaming agent is monofluorodichloroethane, trichlorofluoromethane or trichlorotrifluoroethane; still more preferably, the blowing agent is monofluorodichloroethane.
In some embodiments, the foam stabilizer is a silicone-based foam stabilizer; preferably, the foam stabilizer is polyurethane hard foam silicone oil AK-158 silicone oil, AK-8805 polyurethane foam stabilizer or Demeishi wound silicone oil AK8803; further preferably, the foam stabilizer is dimesh silicone oil AK8803.
In some embodiments, the flame retardant is any one or a combination of several of tributyl phosphate, tri (2-ethylhexyl) phosphate, tri (2-chloroethyl) phosphate, tri (2, 3-dichloropropyl) phosphate, tri (2, 3-dibromopropyl) phosphate, pyrol99, toluene-diphenyl phosphate, tricresyl phosphate, triphenyl phosphate, 2-ethylhexyl-diphenyl phosphate, bis (4-hydroxyphenyl) phenylphosphine oxide, and casein; preferably, the flame retardant is Pyrol99.
In some embodiments, the polymeric MDI has a-NCO content of 30 to 35wt%.
The application of the spray-type polyurethane hard foam composition in preparing spray-type polyurethane hard foam is also within the protection scope of the invention.
Specifically, the material A and the material B are added into a mixing chamber of a spraying machine, are stirred at the temperature of 50-80 ℃ and the rotating speed of 200-300 rpm, are sprayed and foamed after being mixed, and are solidified within 2 minutes after being sprayed, so that the spray-type polyurethane hard foam is obtained.
Specifically, preferably, the material A and the material B are added into a mixing chamber of a spraying machine, are stirred at the temperature of 60-70 ℃ and the rotating speed of 200-300 rpm, are sprayed and foamed after being mixed, and are solidified within 2 minutes after being sprayed, so that the spray-type polyurethane hard foam is obtained.
Specifically, the molar ratio of hydroxyl groups in the vegetable oil polyol in the A material to-NCO in the polymeric MDI in the B material is 1:1.1 to 1.3, preferably 1:1.2.
the application of the spray-type polyurethane hard foam composition in preparing tunnel thermal insulation materials is also within the protection scope of the invention.
The beneficial effects are that:
the invention adopts vegetable oil polyol with specific hydroxyl value as raw material, and the prepared bio-based polyurethane hard foam has good adhesive property and mechanical property, and simultaneously has good heat preservation and water insulation effects. The novel compounding and catalyzing system is adopted, the prepared spraying type bio-based polyurethane hard foam has short reaction time, and the spraying type bio-based polyurethane hard foam can be obtained by solidification within 2 minutes after spraying and foaming, so that the requirements of site construction can be met.
Detailed Description
The invention will be better understood from the following examples. However, it will be readily appreciated by those skilled in the art that the description of the embodiments is provided for illustration only and should not limit the invention as described in detail in the claims.
The vegetable oil polyol used in this example was prepared according to the prior art (chinese patent application No. 201310247746.8).
The polymeric MDI used in the examples of the present invention was purchased from tabacco vanity polyurethane stock.
The method for relevant determination of the prepared vegetable oil polyol and polyurethane material is as follows:
(1) The closed cell content was determined according to GB/T10799-2008.
(2) Compressive strength was measured according to GB/T8813-2008.
(3) Oxygen index was determined according to GB/T2406-1993.
(4) The monomer burn test was determined according to GB/T20284-2006.
(5) Combustion performance was determined according to GB 8624-2012.
(6) Combustion behaviour was determined according to GB/T2406.2-2009.
(7) Flammability experiments were determined according to GB/T8626-2007.
(8) The adhesive strength, tensile strength and water impermeability of the spray-coated rigid polyurethane were determined according to GB 50404-2017.
(9) The thermal insulation properties of the sprayed rigid polyurethane were determined according to GB/T10294-2008.
Example 1
100g of soybean oil polyol (hydroxyl value is 312mg KOH/g) is uniformly mixed with 0.5g of imidazole type ionic liquid catalyst (anion is dicyandiamide radical and cation is CB-5), 3g of foaming agent monofluorodichloroethane, 2g of foam stabilizer Demeishi silicone oil AK8803 and 15g of flame retardant Pyrol99 to be used as a material A; the B material was a polymeric MDI having an 88g-NCO content of 32% by weight. And (3) adding the material A and the material B into a mixing chamber of a spraying machine, stirring at the temperature of 60-70 ℃ and the rotating speed of 200-300 rpm, spraying the mixture on a plate for on-site foaming after mixing, and obtaining the spray-type polyurethane rigid foam after solidification.
Example 2
100g of soybean oil polyol (hydroxyl value is 383mg KOH/g) is uniformly mixed with 0.5g of imidazole type ionic liquid catalyst (anion is dicyandiamide radical and cation is CB-5), 3g of foaming agent monofluoro dichloroethane, 2g of foam stabilizer Demeishi silicone oil AK8803 and 15g of flame retardant Pyrol99 to be used as a material A; the B material was 108g of polymeric MDI having an NCO content of 32% by weight. And (3) adding the material A and the material B into a mixing chamber of a spraying machine, stirring at the temperature of 60-70 ℃ and the rotating speed of 200-300 rpm, spraying the mixture on a plate for on-site foaming after mixing, and obtaining the spray-type polyurethane rigid foam after solidification.
Example 3
100g of soybean oil polyol (hydroxyl value is 427mg KOH/g) is uniformly mixed with 0.5g of imidazole type ionic liquid catalyst (anion is dicyandiamide radical and cation is CB-5), 3g of foaming agent monofluorodichloroethane, 2g of foam stabilizer Demeishi silicone oil AK8803 and 15g of flame retardant Pyrol99 to be used as a material A; the B material was 120g of polymeric MDI having an NCO content of 32% by weight. And (3) adding the material A and the material B into a mixing chamber of a spraying machine, stirring at the temperature of 60-70 ℃ and the rotating speed of 200-300 rpm, spraying the mixture on a plate for on-site foaming after mixing, and obtaining the spray-type polyurethane rigid foam after solidification.
Example 4
100g of soybean oil polyol (hydroxyl value is 489mg KOH/g) is uniformly mixed with 0.5g of imidazole type ionic liquid catalyst (anion is dicyandiamide root, cation is CB-5), 3g of foaming agent monofluoro dichloroethane, 2g of foam stabilizer Demeishi silicone oil AK8803 and 15g of flame retardant Pyrol99 to be used as a material A; the B material was a polymeric MDI having 137g-NCO content of 32% by weight. And (3) adding the material A and the material B into a mixing chamber of a spraying machine, stirring at the temperature of 60-70 ℃ and the rotating speed of 200-300 rpm, spraying the mixture on a plate for on-site foaming after mixing, and obtaining the spray-type polyurethane rigid foam after solidification.
Comparative example 1
100g of soybean oil polyol (hydroxyl value is 312mg KOH/g) is uniformly mixed with 0.5g of imidazole type ionic liquid catalyst (anion is dicyandiamide radical and cation is CB-5), 3g of foaming agent monofluorodichloroethane, 2g of foam stabilizer Demeishi silicone oil AK8803 and 15g of flame retardant Pyrol99 to be used as a material A; the B material was a polymeric MDI having an 80g-NCO content of 32% by weight. And (3) adding the material A and the material B into a mixing chamber of a spraying machine, stirring at the temperature of 60-70 ℃ and the rotating speed of 200-300 rpm, spraying the mixture on a plate for on-site foaming after mixing, and obtaining the spray-type polyurethane rigid foam after solidification.
Comparative example 2
100g of soybean oil polyol (hydroxyl value is 383mg KOH/g) is uniformly mixed with 0.5g of imidazole type ionic liquid catalyst (anion is dicyandiamide radical and cation is CB-5), 3g of foaming agent monofluoro dichloroethane, 2g of foam stabilizer Demeishi silicone oil AK8803 and 15g of flame retardant Pyrol99 to be used as a material A; the B material was 134g of polymeric MDI having an NCO content of 32% by weight. And (3) adding the material A and the material B into a mixing chamber of a spraying machine, stirring at the temperature of 60-70 ℃ and the rotating speed of 200-300 rpm, spraying the mixture on a plate for on-site foaming after mixing, and obtaining the spray-type polyurethane rigid foam after solidification.
Comparative example 3
100g of soybean oil polyol (hydroxyl value is 427mg KOH/g) is uniformly mixed with 0.5g of imidazole type ionic liquid catalyst (anion is dicyandiamide radical and cation is CB-5), 3g of foaming agent monofluorodichloroethane, 2g of foam stabilizer Demeishi silicone oil AK8803 and 5g of flame retardant Pyrol99 to be used as a material A; the B material was 120g of polymeric MDI having an NCO content of 32% by weight. And (3) adding the material A and the material B into a mixing chamber of a spraying machine, stirring at the temperature of 60-70 ℃ and the rotating speed of 200-300 rpm, spraying the mixture on a plate for on-site foaming after mixing, and obtaining the spray-type polyurethane rigid foam after solidification.
Comparative example 4
100g of soybean oil polyol (hydroxyl value is 489mg KOH/g) is uniformly mixed with 0.5g of imidazole type ionic liquid catalyst (anion is dicyandiamide root, cation is CB-5), 3g of foaming agent monofluoro dichloroethane, 2g of foam stabilizer Demeishi silicone oil AK8803 and 30g of flame retardant Pyrol99 to be used as a material A; the B material was a polymeric MDI having 137g-NCO content of 32% by weight. And (3) adding the material A and the material B into a mixing chamber of a spraying machine, stirring at the temperature of 60-70 ℃ and the rotating speed of 200-300 rpm, spraying the mixture on a plate for on-site foaming after mixing, and obtaining the spray-type polyurethane rigid foam after solidification.
Comparative example 5
Uniformly mixing 100g of soybean oil polyol (the hydroxyl value is 383mg KOH/g), 0.5g of triethylamine, 3g of foaming agent monofluorodichloroethane, 2g of foam stabilizer Demeishichuang silicone oil AK8803 and 15g of flame retardant Pyrol99 to obtain a material A; the B material was 108g of polymeric MDI having an NCO content of 32% by weight. And (3) adding the material A and the material B into a mixing chamber of a spraying machine, stirring at the temperature of 60-70 ℃ and the rotating speed of 200-300 rpm, spraying the mixture on a plate for on-site foaming after mixing, and obtaining the spray-type polyurethane rigid foam after solidification.
Example 5: characterization of properties of vegetable oil-based spray polyurethane hard foam
The performance indexes of the vegetable oil-based spray-type polyurethane hard foam prepared in examples 1 to 4 and comparative examples 1 to 5 are shown in Table 1.
Table 1 performance indexes of spray type polyurethane hard foam prepared in examples 1 to 4 and comparative examples 1 to 5
As can be seen from table 1, in the preparation process of the rigid polyurethane foam of the spray type, (1) the addition of more flame retardant leads to the mechanical properties of the rigid polyurethane foam of the spray type being insufficient (example 4 vs. comparative example 4); (2) The addition of less flame retardant results in poor flame retardant effect of the spray-type polyurethane rigid foam (example 3vs comparative example 3); (3) The ratio of materials A and B will have an effect on the mechanical properties of the hard foam (example 1 vs. example 1, example 2 vs. example 2); (4) The type of catalyst affects the reaction time and the properties of the hard foam produced (example 2 vs. comparative example 5).
The invention provides a spray-type polyurethane hard foam composition and a thought and a method for applying the same, and the method and the way for realizing the technical scheme are numerous, the above is only a preferred embodiment of the invention, and it should be pointed out that a plurality of improvements and modifications can be made to a person skilled in the art without departing from the principle of the invention, and the improvements and the modifications are also considered as the protection scope of the invention. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (10)
1. The spray-type polyurethane hard foam composition is characterized by comprising a material A and a material B, wherein the material A and the material B are respectively and independently packaged;
the material A comprises the following components in parts by weight:
100 parts of vegetable oil polyol;
0.1-1 part of ionic liquid catalyst;
1-5 parts of foaming agent;
1-3 parts of foam stabilizer;
10-20 parts of flame retardant;
the material B is polymeric MDI;
preferably, the material A comprises the following components in parts by weight:
100 parts of vegetable oil polyol;
0.2 to 0.6 portion of ionic liquid catalyst;
3 parts of foaming agent;
2 parts of foam stabilizer;
15 parts of flame retardant;
the material B is polymeric MDI;
wherein the material A does not contain a cross-linking agent and water; the material B does not contain a cross-linking agent and water.
2. The spray-on polyurethane hard foam composition according to claim 1, wherein the vegetable oil polyol is any one or a combination of several of olive oil polyol, peanut oil polyol, rapeseed oil polyol, cottonseed oil polyol, soybean oil polyol, coconut oil polyol, palm oil polyol, sesame oil polyol, corn oil polyol and sunflower oil polyol, preferably soybean oil polyol; the hydroxyl value of the vegetable oil polyol is 300-500 mg KOH/g.
3. The spray-on polyurethane rigid foam composition according to claim 1, wherein the ionic liquid catalyst is a pyridine-type ionic liquid catalyst, an imidazole-type ionic liquid catalyst, or a long-chain aliphatic amine-type ionic liquid catalyst; the anion of the ionic liquid catalyst is Bronsted alkali; the Bronsted base is dicyandiamide radical, hexafluorophosphate radical, boron tetrafluoride ion or bis-trifluoromethanesulfonyl imide radical, preferably dicyandiamide radical; the cation of the ionic liquid catalyst is preferably any one of cations shown in the following structures:
further preferred is
4. The spray-on polyurethane hard foam composition according to claim 1, wherein the foaming agent is any one or a combination of two of a physical foaming agent and a chemical foaming agent; the foam stabilizer is an organosilicon foam stabilizer.
5. The spray-type polyurethane hard foam composition according to claim 1, wherein the flame retardant is any one or a combination of several of tributyl phosphate, tri (2-ethylhexyl) phosphate, tri (2-chloroethyl) phosphate, tri (2, 3-dichloropropyl) phosphate, tri (2, 3-dibromopropyl) phosphate, pyrol99, toluene-diphenyl phosphate, tricresyl phosphate, triphenyl phosphate, 2-ethylhexyl-diphenyl phosphate, bis (4-hydroxyphenyl) phenylphosphine oxide and casein; preferably, the flame retardant is Pyrol99.
6. The spray-on polyurethane rigid foam composition according to claim 1, characterized in that the polymeric MDI has an NCO content of 30 to 35wt%.
7. Use of a spray-on polyurethane hard foam composition according to any one of claims 1 to 6 for the preparation of spray-on polyurethane hard foam.
8. The method according to claim 7, wherein the material A and the material B are added into a mixing chamber of a spraying machine, stirred at a speed of 200-300 rpm at 50-80 ℃, sprayed and foamed after being mixed, and cured within 2min after being sprayed, so as to obtain the spray-type polyurethane hard foam.
9. The use according to claim 7, wherein the molar ratio of hydroxyl groups in the vegetable oil polyol in the a batch to-NCO in the polymeric MDI in the B batch is 1:1.1 to 1.3, preferably 1:1.2.
10. use of the spray-type polyurethane rigid foam composition according to any one of claims 1 to 6 for preparing a tunnel insulation material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311620956.7A CN117700663A (en) | 2023-11-30 | 2023-11-30 | Spray-type polyurethane hard foam composition and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311620956.7A CN117700663A (en) | 2023-11-30 | 2023-11-30 | Spray-type polyurethane hard foam composition and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117700663A true CN117700663A (en) | 2024-03-15 |
Family
ID=90154349
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311620956.7A Pending CN117700663A (en) | 2023-11-30 | 2023-11-30 | Spray-type polyurethane hard foam composition and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117700663A (en) |
-
2023
- 2023-11-30 CN CN202311620956.7A patent/CN117700663A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101519485B (en) | Wide temperature domain damping polyurethane micropore elastomer material and preparation method thereof | |
| JP5547722B2 (en) | Method for producing rigid polyisocyanurate foam using natural oil polyol | |
| CN110396166B (en) | Polyurethane foam with good heat insulation property and preparation method thereof | |
| CN102558482B (en) | Environment-friendly flame-retardant polyurethane wood-imitation material | |
| CN103467694B (en) | A kind of polyurethane plate and preparation method thereof | |
| CN107602817A (en) | A kind of high cold-resistant polyurethane shock pad and preparation method thereof | |
| CN104151517A (en) | High-flame-retardant polyurethane modified polyisocyanurate hard foam thermal insulation material of external wall and preparation method of thermal insulation material | |
| CN104672420A (en) | High-strength polyurethane rigid foam as well as preparation method and application thereof | |
| CN108948410B (en) | Polyol composition and polyurethane rigid foam prepared from same | |
| CN107033317A (en) | A kind of hard polyurethane foam material and preparation method and application | |
| CN108997613A (en) | A kind of multicomponent composite halogen-free flame retarded rigid polyurethane foams accessing phospho hetero phenanthrene group | |
| CN111138622A (en) | Organic polymer ultralow-temperature reinforcing material for coal rock mass | |
| CN111286004B (en) | Hydrophobic polyurethane anti-condensation air-tight sealing material and preparation method thereof | |
| CN111777854A (en) | Novel environment-friendly flame-retardant polyurethane grouting material and preparation method thereof | |
| CN114835872A (en) | High-flame-retardance low-heat-conductivity polyurethane foam material and preparation method thereof | |
| CN110903454A (en) | Modified polyurethane foam material and preparation method and application thereof | |
| CN105384902B (en) | A kind of building heat preservation novel environment friendly flame retardant polyurethane material | |
| CN107298748B (en) | Environment-friendly degradable flame-retardant polyurethane rapid packaging material and preparation method thereof | |
| CN117700663A (en) | Spray-type polyurethane hard foam composition and application thereof | |
| CN112266463B (en) | Flame-retardant lignin-based rigid polyurethane foam for automotive interior and preparation method thereof | |
| CN108102346A (en) | A kind of flame retarded rigid polyurethane foams feedstock composition | |
| CN107880250A (en) | Fuel transmission deep cooling pipeline hard polyaminoester composite and preparation method thereof | |
| CN114015004B (en) | Shock-absorbing polyurea rigid foam material and preparation method and application thereof | |
| CN107474209B (en) | Foam composition, polyurethane plastic, and preparation method and application of polyurethane plastic | |
| CN111100444A (en) | Preparation method of flame-retardant polyurethane foam plastic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |