CN105504223A - Chromic-acid-resistant polyurethane elastomer and preparation method thereof - Google Patents
Chromic-acid-resistant polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN105504223A CN105504223A CN201511031228.8A CN201511031228A CN105504223A CN 105504223 A CN105504223 A CN 105504223A CN 201511031228 A CN201511031228 A CN 201511031228A CN 105504223 A CN105504223 A CN 105504223A
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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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
- C08G18/6674—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
- C08G18/65—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
- C08G18/6677—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 having at least three hydroxy groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
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Abstract
The invention relates to a chromic-acid-resistant polyurethane elastomer and a preparation method thereof, and belongs to the technical field of application of polyurethane elastomer. The chromic-acid-resistant polyurethane elastomer consists of a component A and a component B, and the weight ratio of the component A to the component B is 100:(2.9-6.2), wherein the component A is a polyurethane prepolymer, and is prepared from polytetrahydrofuran ether glycol, a diisocyanate plasticizer and an antioxidant; the component B is a curing agent and is one or two of 1,4-butanediol or trimethylolpropane. The functionality of the polytetrahydrofuran ether glycol is 2, and the number-average molecular weight of the polytetrahydrofuran ether glycol is 1000-2000. The chromic-acid-resistant polyurethane elastomer provided by the invention has relatively good chromic acid resistance, and after the product is soaked for 24 hours in a chromic acid environment, the property conservation percentage of the product is relatively good; the invention simultaneously provides a preparation method which is simple, feasible, energy-saving and environment-friendly.
Description
Technical field
The present invention relates to a kind of polyurethane elastomer of resistance to chromic acid and preparation method thereof, belong to polyurethane elastomer applied technical field.
Background technology
Polyurethane elastomer is a kind of high molecular synthetic material between plastics and rubber, has the performance such as excellent wear resistance, good mechanical strength and oil resistant, low temperature resistant, resistance to ozone ageing, is thus widely used in the fields such as rubber roll, oil sealing, doughnut.Urethane has been deep in national economy and people's lives, becomes one and develops synthetic materials rapidly.Polyurethane rubber roller has that tear resistance is excellent, rebound performance good, and wear resisting property is good, long service life, can bear the advantage such as high pressure, high-revolving environment, is widely used in steel mill, papermaking, printing industry.Such as, but for the application of some particular surroundingss, be used in the rubber roll in chromic acid environment, because chromic acid has acidity and oxidisability, general polyurethane material decomposes very fast in the environment of chromic acid, and degradation is more, causes the property retention rate of product low.Research and develop the needs that the polyurethane elastomer of resistance to chromic acid is the progress of reply market requirement boosting elastomeric technology.
Summary of the invention
The object of this invention is to provide a kind of polyurethane elastomer of resistance to chromic acid, it has good resistance to chromic acid performance, and soak 24 hours in the environment of chromic acid, the property retention rate of product is better; Invention also provides preparation method that is simple, energy-conserving and environment-protective.
The polyurethane elastomer of resistance to chromic acid of the present invention, is made up of component A and B component, and the weight ratio of A, B component is 100:2.9 ~ 6.2, wherein:
(1) component A is polyurethane prepolymer, is made up of the raw material of following weight percentage:
(2) B component is solidifying agent, is one or both in BDO or TriMethylolPropane(TMP) (TMP);
The functionality of described PTMG is 2, and number-average molecular weight is 1000-2000.
Described vulcabond is by 2,4-diphenylmethanediisocyanate and 4,4'-diphenylmethanediisocyanate (MDI-50), 4, one or more in the MDI (liquefied mdi) of 4 '-diphenylmethanediisocyanate (MDI-100) or Carbodiimide-Modified mix.
Described softening agent is dioctyl terephthalate (DOTP), dioctyl phthalate (DOP) (DOP), dimethyl glycol phthalate (DMEP), diisobutyl phthalate (DIBP) or butyl benzyl phthalate (BBP).
Described oxidation inhibitor is 1076,1010, PDP or 1035.
The described method for preparing polyurethane elastic body of resistance to chromic acid, comprises the following steps:
(1) component A is prepared: by PTMG, vulcabond, softening agent and oxidation inhibitor 70 ~ 85 DEG C of reactions 2 ~ 3 hours, obtain polyurethane prepolymer, its isocyano-content is 2.7 ~ 6.0%;
(2) polyurethane elastomer is prepared: polyurethane prepolymer is heated to 80 ~ 90 DEG C, again it is mixed with the solidifying agent being heated to 50 ~ 60 DEG C, then mixture is poured in the mould of 100 ~ 150 DEG C, the demoulding after 6 ~ 10h, by the sulfuration 8 ~ 10 hours at 100 ~ 120 DEG C of the goods after the demoulding, obtain the polyurethane elastomer of resistance to chromic acid, its hardness is Shao A35 ~ 70.
The present invention is in the process of preparation component A, and the collocation of raw material PTMG and MDI uses, and makes product have excellent resistance to chromic acid performance; In the preparation process of polyurethane elastomer, the use of BDO, TMP and softening agent makes product have lower hardness.
The present invention has following beneficial effect:
(1) the obtained polyurethane elastomer of resistance to chromic acid, has good resistance to chromic acid performance, and soak 24 hours in the environment of chromic acid, the property retention rate of product is better;
(2) method for preparing polyurethane elastic body of resistance to chromic acid described in, not only energy-conserving and environment-protective, and simple.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, but it does not limit enforcement of the present invention.
In embodiment, material therefor is as follows:
PTMG1000: number-average molecular weight 1000, PTMG;
PTMG2000: number-average molecular weight 2000, PTMG;
MDI-50:2,4-diphenylmethanediisocyanate and 4,4'-diphenylmethanediisocyanate;
MDI-100:4,4'-diphenylmethanediisocyanate;
Liquefied mdi: the MDI of Carbodiimide-Modified;
DOTP: dioctyl terephthalate;
BDO:1,4-butyleneglycol;
TMP: TriMethylolPropane(TMP);
Oxidation inhibitor: 1076.
Percentage ratio in following examples all refers to mass percent.
Embodiment 1
The described method for preparing polyurethane elastic body of resistance to chromic acid, comprises the following steps:
(1) component A is prepared: by the MDI (liquefied mdi) 18.1% of the PTMG (PTMG1000) 63.6% of molecular weight 1000, diphenylmethanediisocyanate (MDI-100) 18.1%, Carbodiimide-Modified, oxidation inhibitor (1076) 0.2% 70 DEG C of reactions 2 hours, vacuum (-0.095MPa) removes bubble, obtain polyurethane prepolymer, its isocyano-content is 6.0%;
(2) polyurethane elastomer is prepared: polyurethane prepolymer is heated to 80 DEG C, again it is mixed with the solidifying agent (mass ratio of BDO and TMP is 4:1) being heated to 50 DEG C, the mass ratio of polyurethane prepolymer and solidifying agent is 100:6.2, then mixture is poured in the mould of 130 DEG C, the demoulding after 6h, by the sulfuration 10 hours at 120 DEG C of the goods after the demoulding, obtain the polyurethane elastomer of resistance to chromic acid, its hardness is Shao A70.
Embodiment 2
The described method for preparing polyurethane elastic body of resistance to chromic acid, comprises the following steps:
(1) component A is prepared: by the PTMG (PTMG2000) 74% of molecular weight 2000, diphenylmethanediisocyanate (MDI-50) 25.7%, oxidation inhibitor (1076) 0.3% 85 DEG C of reactions 3 hours, vacuum (-0.095MPa) removes bubble, obtain polyurethane prepolymer, its isocyano-content is 5.5%;
(2) polyurethane elastomer is prepared: polyurethane prepolymer is heated to 80 DEG C, again it is mixed with the solidifying agent (TMP) being heated to 60 DEG C, the mass ratio of polyurethane prepolymer and solidifying agent is 100:5.7, then mixture is poured in the mould of 100 DEG C, the demoulding after 7h, by the sulfuration 10 hours at 120 DEG C of the goods after the demoulding, obtain the polyurethane elastomer of resistance to chromic acid, its hardness is Shao A65.
Embodiment 3
The described method for preparing polyurethane elastic body of resistance to chromic acid, comprises the following steps:
(1) component A is prepared: by the MDI (liquefied mdi) 12.2% of the PTMG (PTMG2000) 75.2% of molecular weight 2000, diphenylmethanediisocyanate (MDI-50) 12.2%, Carbodiimide-Modified, oxidation inhibitor (1076) 0.4% 75 DEG C of reactions 2.5 hours, vacuum (-0.095MPa) removes bubble, obtain polyurethane prepolymer, its isocyano-content is 4.5%;
(2) polyurethane elastomer is prepared: polyurethane prepolymer is heated to 85 DEG C, again it is mixed with the solidifying agent (mass ratio of BDO and TMP is 3:7) being heated to 60 DEG C, the mass ratio of polyurethane prepolymer and solidifying agent is 100:4.7, then mixture is poured in the mould of 130 DEG C, the demoulding after 8h, by the sulfuration 10 hours at 110 DEG C of the goods after the demoulding, obtain the polyurethane elastomer of resistance to chromic acid, its hardness is Shao A55.
Embodiment 4
The described method for preparing polyurethane elastic body of resistance to chromic acid, comprises the following steps:
(1) component A is prepared: by the PTMG (PTMG2000) 61.1% of molecular weight 2000, diphenylmethanediisocyanate (MDI-50) 18.4%, dioctyl terephthalate (DOTP) 20%, oxidation inhibitor (1076) 0.5% 85 DEG C of reactions 2 hours, vacuum (-0.095MPa) removes bubble, obtain polyurethane prepolymer, its isocyano-content is 4.5%;
(2) polyurethane elastomer is prepared: polyurethane prepolymer is heated to 90 DEG C, again it is mixed with the solidifying agent (mass ratio of BDO and TMP is 3:7) being heated to 60 DEG C, the mass ratio of polyurethane prepolymer and solidifying agent is 100:3.8, then mixture is poured in the mould of 140 DEG C, the demoulding after 9h, by the sulfuration 8 hours at 120 DEG C of the goods after the demoulding, obtain the polyurethane elastomer of resistance to chromic acid, its hardness is Shao A45.
Embodiment 5
The described method for preparing polyurethane elastic body of resistance to chromic acid, comprises the following steps:
(1) component A is prepared: by the MDI (liquefied mdi) 15.6% of the PTMG (PTMG2000) 44% of molecular weight 2000, Carbodiimide-Modified, dioctyl terephthalate (DOTP) 40%, oxidation inhibitor (1076) 0.4% 75 DEG C of reactions 2 hours, vacuum (-0.095MPa) removes bubble, obtain polyurethane prepolymer, its isocyano-content is 4.5%;
(2) polyurethane elastomer is prepared: polyurethane prepolymer is heated to 90 DEG C, again it is mixed with the solidifying agent (mass ratio of BDO and TMP is 4:1) being heated to 50 DEG C, the mass ratio of polyurethane prepolymer and solidifying agent is 100:2.9, then mixture is poured in the mould of 150 DEG C, the demoulding after 10h, by the sulfuration 9 hours at 120 DEG C of the goods after the demoulding, obtain the polyurethane elastomer of resistance to chromic acid, its hardness is Shao A35.
By the performance of the polyurethane elastomer of embodiment gained in table 1.
The performance of the polyurethane elastomer of table 1 embodiment 1-5 gained
Claims (7)
1. the polyurethane elastomer of resistance to chromic acid, is characterized in that: be made up of component A and B component, and the weight ratio of A, B component is 100:2.9 ~ 6.2, wherein:
(1) component A is polyurethane prepolymer, is made up of the raw material of following weight percentage:
(2) B component is solidifying agent, is one or both in BDO or TriMethylolPropane(TMP);
The functionality of described PTMG is 2, and number-average molecular weight is 1000-2000.
2. the polyurethane elastomer of resistance to chromic acid according to claim 1, it is characterized in that: vulcabond is by 2,4-diphenylmethanediisocyanate and 4,4'-diphenylmethanediisocyanate, 4, one or more in the MDI of 4 '-diphenylmethanediisocyanate or Carbodiimide-Modified mix.
3. the polyurethane elastomer of resistance to chromic acid according to claim 1, is characterized in that: softening agent is dioctyl terephthalate, dioctyl phthalate (DOP), dimethyl glycol phthalate, diisobutyl phthalate or butyl benzyl phthalate.
4. the polyurethane elastomer of resistance to chromic acid according to claim 1, is characterized in that: oxidation inhibitor is 1076,1010, PDP or 1035.
5. the method for preparing polyurethane elastic body of resistance to chromic acid according to claim 1, is characterized in that comprising the following steps:
(1) component A is prepared: by PTMG, vulcabond, softening agent and oxidation inhibitor 70 ~ 85 DEG C of reactions 2 ~ 3 hours, obtain polyurethane prepolymer;
(2) polyurethane elastomer is prepared: polyurethane prepolymer is heated to 80 ~ 90 DEG C, again it is mixed with the solidifying agent being heated to 50 ~ 60 DEG C, then mixture is poured in the mould of 100 ~ 150 DEG C, the demoulding after 6 ~ 10h, by the sulfuration 8 ~ 10 hours at 100 ~ 120 DEG C of the goods after the demoulding, obtain the polyurethane elastomer of resistance to chromic acid.
6. the method for preparing polyurethane elastic body of resistance to chromic acid according to claim 5, is characterized in that: the isocyano-content of polyurethane prepolymer is 2.7 ~ 6.0%.
7. the method for preparing polyurethane elastic body of resistance to chromic acid according to claim 5, is characterized in that: the hardness of the polyurethane elastomer of obtained resistance to chromic acid is Shao A35 ~ 70.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511031228.8A CN105504223A (en) | 2015-12-31 | 2015-12-31 | Chromic-acid-resistant polyurethane elastomer and preparation method thereof |
| PCT/CN2016/082281 WO2017113568A1 (en) | 2015-12-31 | 2016-05-17 | Chromic acid-resistant polyurethane elastomer and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511031228.8A CN105504223A (en) | 2015-12-31 | 2015-12-31 | Chromic-acid-resistant polyurethane elastomer and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106854273A (en) * | 2016-12-31 | 2017-06-16 | 山东诺威聚氨酯股份有限公司 | Polyurethane foamed composite material for high-performance tire and preparation method thereof |
| WO2017113568A1 (en) * | 2015-12-31 | 2017-07-06 | 山东一诺威聚氨酯股份有限公司 | Chromic acid-resistant polyurethane elastomer and preparation method thereof |
| CN108869549A (en) * | 2018-04-11 | 2018-11-23 | 启东海大聚龙新材料科技有限公司 | A kind of multi-layer wear-resistant material and the preparation method and application thereof |
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| CN102199269A (en) * | 2011-03-21 | 2011-09-28 | 黎明化工研究院 | Heat-resistant thermoplastic polyurethane elastomer and preparation method thereof |
| CN102516495A (en) * | 2011-10-27 | 2012-06-27 | 山东东大一诺威聚氨酯有限公司 | Method for preparing corrosion-resisting polyurethane elastomer |
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| US6562932B1 (en) * | 2001-10-12 | 2003-05-13 | Bayer Corporation | Light stable one-shot urethane-urea elastomers |
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| WO2017113568A1 (en) * | 2015-12-31 | 2017-07-06 | 山东一诺威聚氨酯股份有限公司 | Chromic acid-resistant polyurethane elastomer and preparation method thereof |
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| CN108869549A (en) * | 2018-04-11 | 2018-11-23 | 启东海大聚龙新材料科技有限公司 | A kind of multi-layer wear-resistant material and the preparation method and application thereof |
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| WO2017113568A1 (en) | 2017-07-06 |
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