CN105504217B - A kind of self-plasticization type modified high-molecular rotational moulding material and its preparation - Google Patents
A kind of self-plasticization type modified high-molecular rotational moulding material and its preparation Download PDFInfo
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- CN105504217B CN105504217B CN201511035091.3A CN201511035091A CN105504217B CN 105504217 B CN105504217 B CN 105504217B CN 201511035091 A CN201511035091 A CN 201511035091A CN 105504217 B CN105504217 B CN 105504217B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
- C08G18/2825—Alkanols, cycloalkanols or arylalkanols including terpenealcohols having at least 6 carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
Abstract
The present invention provides a kind of self-plasticization type modified high-molecular rotational moulding material, which is characterized in that the raw material including following mass fraction is prepared: 10-16 parts of pla-pcl；12-20 parts of polytetrahydrofuran；1-3 parts of crosslinking agent with isocyanate group；6-15 parts of modifying diisocyanates；0-1 parts of pigment.Plasticizer is grafted by the advantages of present invention combination pla-pcl, polytetrahydrofuran material by diisocyanate as crosslinking agent with them, and formation had not only had flexility but also had plasticizing rigid macromolecule rotational moulding material.
Description
Technical field
The present invention relates to a kind of self-plasticization type modified high-molecular rotational moulding material and its preparations.
Background technique
Polytetrahydrofuran is a kind of high molecular material haveing excellent performance, and product density made from polytetrahydrofuran is high, is had
Good flexibility and anti-hydrolytic performance, anti-aging property is good, and mechanical property is good, but as medical material, flexibility and punching
It hits that toughness is not ideal enough, limits the application to it.
Polycaprolactone Polycaprolactone (abbreviation PCL) is by 6-caprolactone in metallo-organic compound (such as four benzene
Catalyst Ji Xi) is made, ring-opening polymerisation forms under the conditions of dihydroxy or trihydroxy make initiator, belongs to aggretion type polyester, molecule
It measures different and different with the type and dosage of starting material from discrimination degree.PCL is a kind of acyclic straight polyester, and Tg is -60 DEG C, non-
It is often soft, there is great extensibility.But its intensity is not high, also limits the application to it.
Summary of the invention
The problem to be solved in the present invention is to provide a kind of self-plasticization type modified high-molecular rotational moulding materials.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of self-plasticization type modified high-molecular rotational moulding
Material, which is characterized in that the raw material including following mass fraction is prepared:
The sum of the molal quantity for the total hydroxyl for including in above-mentioned raw materials, and includes total isocyanate group molal quantity and equal.
Preferably, the molecular weight of the pla-pcl is 400-2000；More preferably molecular weight is 1000.
Preferably, the ptmg molecule amount is 1000-2000；More preferably molecular weight is 1000.
Preferably, the crosslinking agent with isocyanate group is naphthenic type diisocyanate；Preferably, (different for two
Cyanate radical closes methyl) hexamethylene, 1, hexamethylene-diisocyanate, 3- isocyanates methylene -3,5,5- trimethylcyclohexyl is different
Cyanate, methyl diphenylene diisocyanate or Toluene-2,4-diisocyanate, one of 4- diisocyanate.
More preferably hexamethylene diisocyanate or two (isocyanatomethyl) hexamethylenes.
Further, the modifying diisocyanates the preparation method comprises the following steps: pla-pcl is mixed with diisocyanate, 80-
After 100 DEG C are stirred to react, it is down to 20-60 DEG C and the small molecular alcohol with plasticization is added, 60-110 DEG C is stirred to react to solution
Clarification, without alcohol steam, after bubble-free, stand to get；Wherein, the OH molal quantity of pla-pcl: NCO moles of diisocyanate
Number: the OH molal quantity of small molecular alcohol is 3:6:1.
The modifying diisocyanates another the preparation method comprises the following steps: pla-pcl is mixed with a part of diisocyanate,
After 80-100 DEG C is stirred to react, it is down to 20-60 DEG C and the small molecular alcohol with plasticization is added, 60-110 DEG C is stirred to react, after
It is continuous to be added remaining diisocyanate, 100 DEG C of stirrings to solution clarification, without alcohol steam, after bubble-free, stand to get；Wherein,
The OH molal quantity of pla-pcl: twice be added diisocyanate NCO molal quantity and: the OH molal quantity of small molecular alcohol be 3:9:1.
Preferably, the NCO molal quantity for the diisocyanate being added for the first time: the OH molal quantity of pla-pcl is 2:1.
In two kinds of preparation methods, the pla-pcl for being used to prepare modifying diisocyanates includes trihydroxy functional group,
Molecular weight is 540.The small molecular alcohol with plasticization for being used to prepare modifying diisocyanates is isooctanol.The use
In prepare modifying diisocyanates diisocyanate be hexamethylene diisocyanate or Toluene-2,4-diisocyanate, 4- diisocyanate.
Another object of the present invention is to provide a kind of sides for preparing the self-plasticization type modified high-molecular rotational moulding material
Method includes the following steps: to mix raw material, electromagnetic agitation, at 70-80 DEG C, vacuumizes, then the rotational moulding at 210 DEG C is soaked cold
But to get.
Further, the rotational moulding time is 12min, 30 turns/min of revolving speed；Cooling time is 180s.
All number marks of the present invention, such as pH, temperature, time, concentration, including range, are all approximations.It is all
" being equal to " is also all approximately equal.It is to be understood that although all plus term before always not describing all number marks explicitly
" about ".It will also be understood that, although not always specific narration, reagent described herein is only example, and equivalent is simultaneously
It is known in the art.
The advantages and positive effects of the present invention are: the advantages of present invention combination pla-pcl, polytetrahydrofuran material,
By diisocyanate as crosslinking agent, plasticizer is grafted with them, formation had not only had flexility but also had plasticizing rigidity
Macromolecule rotational moulding material.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of self-plasticization type modified high-molecular rotational moulding material.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that the present embodiment is served only for pair
The present invention is further described, and should not be understood as limiting the scope of the invention, and the person skilled in the art in the field can
The modifications and adaptations of some essence are made with the content according to foregoing invention.
The preparation of 1 modifying diisocyanates of embodiment
Pla-pcl (the molal quantity: 0.1352 for being 540 by the 73.03g amount of molecule of functional group containing trihydroxy；OH molal quantity:
0.4057) with 68.16g hexamethylene diisocyanate (molal quantity: 0.4057；NCO molal quantity: 0.8114) it mixes, 80-100
After DEG C being stirred to react 3 hours, 25 DEG C are down to, 17.58g isooctanol is added and (molal quantity: 0.1352), 0.5h, solution is stirred at room temperature
It is more sticky in colorless and transparent, whiten after stirring and many bubbles occurs.
At this point, be warming up to 110 DEG C of stirring 1.5h reaction, continuously add 39.69g hexamethylene diisocyanate (molal quantity:
0.2363, NCO molal quantity: 0.4725), 100 DEG C of stirring 30min, until solution clarification, without alcohol steam, after bubble-free, stand, i.e.,
?.It is observed at 100 DEG C, solution good fluidity, bubble collapse, solution is clarification by leucismus.
The preparation of 2 modifying diisocyanates of embodiment
Pla-pcl (the molal quantity: 0.05 for being 540 by the 27g amount of molecule of functional group containing trihydroxy；OH molal quantity: 0.15) with
29.1g Toluene-2,4-diisocyanate, 4- diisocyanate (molal quantity: 0.15；NCO molal quantity: 0.300) mixing, after 80-100 DEG C is stirred to react,
Be down to 60 DEG C, be added 6.5g isooctanol (molal quantity 0.05), 60 DEG C are stirred to react 240 minutes, be warming up to 100 DEG C, until substantially without
Isooctanol steam, mobility is fine, basic bubble-free, solution clear, pumping, until solution bubble-free, stops heating, it is quiet
Set to get.Observation overnight, discovery solution is uniform and stable, and flowing slowly, is heated to 80 DEG C, good fluidity at room temperature.
3 self-plasticization type modified high-molecular rotational moulding material of embodiment
Weigh pla-pcl (the OH molal quantity: 0.02018), 1000 molecular weight of 14.20g of 10.09g1000 molecular weight
Polytetrahydrofuran (OH molal quantity: 0.02840), 1.71g hexamethylene diisocyanate (NCO molal quantity: 0.02036), 7.54g
(the NCO molal quantity: 0.02822), 0.40g pigment of modifying diisocyanates made from embodiment 1；At 80 DEG C, electromagnetic agitation 5min,
5min is vacuumized while stirring, is not stirred and is vacuumized 5min.Obtained solution, the rotational moulding 12min at 210 DEG C, 30 turns of revolving speed/
Min, then soak cooling 180s to get.
Obtained rotational moulding material is placed in -20 DEG C of refrigerator to place 24 hours and is observed, material is still soft without any damage
It is soft；It is observed after being placed 24 hours in 80 DEG C of baking oven, material is without any damage, and still soft, weight is not any change, it was demonstrated that
Without plasticizer.
4 self-plasticization type modified high-molecular rotational moulding material of embodiment.
Weigh pla-pcl (the OH molal quantity: 0.02018), 1000 molecular weight of 14.20g of 10.09g1000 molecular weight
Polytetrahydrofuran (OH molal quantity: 0.02840), 1.97g bis- (isocyanatomethyl) hexamethylene (NCO molal quantity:
0.02821), (the NCO molal quantity: 0.02821), 0.40g pigment of modifying diisocyanates made from 9.72g embodiment 2；80℃
Under, electromagnetic agitation 5min vacuumizes 5min while stirring, does not stir and vacuumize 5min.Obtained solution, the rotational moulding at 210 DEG C
12min, 30 turns/min of revolving speed, then soak cooling 180s to get.
Obtained rotational moulding material is placed in -20 DEG C of refrigerator to place 24 hours and is observed, material is still soft without any damage
It is soft；It is observed after being placed 24 hours in 79 DEG C of baking oven, material is without any damage, and still soft, weight is not any change, it was demonstrated that
Without plasticizer.
Effect experimental examples
Embodiment 3,4 obtained self-plasticization type modified high-molecular rotational moulding materials are detected, obtained data are as follows:
| Tensile strength (kpa) | Elongation at break | Shore hardness | |
| Embodiment 3 | 670 | 570% | 18 |
| Embodiment 4 | 686 | 562% | 20 |
As seen from the above table, self-plasticization type modified high-molecular rotational moulding material of the present invention has excellent flexility.
The embodiments of the present invention have been described in detail above, but content is only the preferred embodiment of the present invention,
It should not be considered as limiting the scope of the invention.All changes and improvements made in accordance with the scope of the present invention, should all
It still belongs within this patent covering scope.
Claims (5)
1. a kind of self-plasticization type modified high-molecular rotational moulding material, which is characterized in that the preparation of raw material including following mass fraction and
At:
The molecular weight of the polycaprolactone is 400-2000；
The ptmg molecule amount is 1000-2000；
Crosslinking agent with isocyanate group is two (isocyanatomethyl) hexamethylenes, hexamethylene diisocyanate, 3- isocyanide
Acid esters methylene -3,5,5- trimethylcyclohexylisocyanate, methyl diphenylene diisocyanate or Toluene-2,4-diisocyanate, bis- isocyanide of 4-
One of acid esters；
The modifying diisocyanates the preparation method comprises the following steps: polycaprolactone is mixed with diisocyanate, 80-100 DEG C of stirring is anti-
Ying Hou is down to 20-60 DEG C and the small molecular alcohol with plasticization is added, and 60-110 DEG C is stirred to react to solution clarification, without alcohol steaming
Vapour, after bubble-free, stand to get；Wherein, the OH molal quantity of polycaprolactone: the NCO molal quantity of diisocyanate: small molecular alcohol
OH molal quantity be 3:6:1；The polycaprolactone for being used to prepare modifying diisocyanates includes trihydroxy functional group, molecular weight
It is 540；
Or the modifying diisocyanates the preparation method comprises the following steps: polycaprolactone is mixed with a part of diisocyanate, 80-100
After DEG C being stirred to react, it is down to 20-60 DEG C and the small molecular alcohol with plasticization is added, 60-110 DEG C is stirred to react, and continuously adds
Remaining diisocyanate, 100 DEG C of stirrings to solution clarification, without alcohol steam, after bubble-free, stand to get；Wherein, gather in oneself
The OH molal quantity of ester: twice be added diisocyanate NCO molal quantity and: the OH molal quantity of small molecular alcohol be 3:9:1；The use
Include trihydroxy functional group, molecular weight 540 in the polycaprolactone for preparing modifying diisocyanates；
The small molecular alcohol with plasticization for being used to prepare modifying diisocyanates is isooctanol.
2. modified high-molecular rotational moulding material according to claim 1, it is characterised in that: the molecular weight of the polycaprolactone is
1000。
3. modified high-molecular rotational moulding material according to claim 1, it is characterised in that: the molecular weight of the polytetrahydrofuran
It is 1000.
4. a kind of method for preparing self-plasticization type modified high-molecular rotational moulding material described in claim 1, which is characterized in that including
Following steps: raw material is mixed, electromagnetic agitation, at 70-80 DEG C, is vacuumized, the rotational moulding at 210 DEG C, then immersion cooling, i.e.,
?.
5. the method according to claim 4 for preparing self-plasticization type modified high-molecular rotational moulding material, it is characterised in that: described
The rotational moulding time is 12min, 30 turns/min of revolving speed；Cooling time is 180s.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6218462B1 (en) * | 1999-12-03 | 2001-04-17 | Bayer Corporation | Liquid ultra-high molecular weight polyurethane plasticizers |
| CN101906283A (en) * | 2010-08-31 | 2010-12-08 | 东莞市普赛达密封粘胶有限公司 | Internal plasticization type mono-component polyurethane seal gum |
| CN105086423A (en) * | 2015-08-31 | 2015-11-25 | 沈阳化工大学 | Low-hardness casted polyurethane elastomer with plasticizer and preparation method for polyurethane elastomer |
-
2015
- 2015-12-31 CN CN201511035091.3A patent/CN105504217B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6218462B1 (en) * | 1999-12-03 | 2001-04-17 | Bayer Corporation | Liquid ultra-high molecular weight polyurethane plasticizers |
| CN101906283A (en) * | 2010-08-31 | 2010-12-08 | 东莞市普赛达密封粘胶有限公司 | Internal plasticization type mono-component polyurethane seal gum |
| CN105086423A (en) * | 2015-08-31 | 2015-11-25 | 沈阳化工大学 | Low-hardness casted polyurethane elastomer with plasticizer and preparation method for polyurethane elastomer |
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