CN107828037A - A kind of TPU materials available for drinking-water pipe and preparation method thereof - Google Patents
A kind of TPU materials available for drinking-water pipe and preparation method thereof Download PDFInfo
- Publication number
- CN107828037A CN107828037A CN201711077686.4A CN201711077686A CN107828037A CN 107828037 A CN107828037 A CN 107828037A CN 201711077686 A CN201711077686 A CN 201711077686A CN 107828037 A CN107828037 A CN 107828037A
- Authority
- CN
- China
- Prior art keywords
- parts
- tpu materials
- diisocyanate
- quaternary ammonium
- prepolymer
- 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
Classifications
-
- 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
- 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
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
-
- 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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a kind of TPU materials available for drinking-water pipe and preparation method thereof.The TPU materials include the following raw material component according to the mass fraction：30 50 parts of diisocyanate, 50 70 parts of PPGs, 5 20 parts of chitosan quaternary ammonium salts, 10 20 parts of chain extenders, 10 20 parts of vulcanizing agents and 0.5 2 parts of catalyst.The TPU materials are by first by PPG and chitosan quaternary ammonium salt mixed dehydration, then with diisocyanate prepolymer, then adding chain extender, vulcanizing agent and catalyst and carrying out chain extending reaction, finally the method for cross-linking curing is prepared at high temperature.TPU materials provided by the invention have higher intensity, resistance to tearing energy, pliability, good cold tolerance and anti-microbial property concurrently, disclosure satisfy that the performance requirement of drinking-water pipe.
Description
Technical field
The invention belongs to TPUE technical field, and in particular to a kind of TPU available for drinking-water pipe
Material and preparation method thereof.
Background technology
From the 1960s, plastic pipe starts to use in feedwater piping.General bore is less to use poly- second
Alkene pipe (PVC), PA tube, larger of bore use polyvinyl chloride pipe more, and PVC-U drinking-water pipe (PVC-u) is exactly it
Middle one kind.
PVC is thermal sensitivity plastics, and heat stabilizer is must be added to when fabricated product to be molded.Heat stabilizer at present
The principal item of application is lead salt stabilizer, organic tin stabilizer, calcium-zinc composite stabilizing agent etc..Due to lead salt stabilizer
There is larger superiority in stability and cost etc., therefore be all the first choice of PVC product heat stabilizer all the time, mesh
Stabilizer is used as using lead salt mostly in preceding domestic PVC processing.Pvc pipe is used generally as drainpipe, and the PVC plastic containing lead salt is given
In use, heavy metal lead can separate out water pipe from pipeline, directly contribute the pollution of drinking water.And PVC is hard modeling
Material, there is the shortcomings that easily becoming fragile cracking at low temperature.
TPUE (TPU) is because with good tensile strength, tearing toughness, impact resistance, wear-resisting
The advantages that property, weatherability, hydrolytic resistance and oil resistivity, it is widely used in flexible pipe, packing ring, wheel belt, roller, gear, pipeline etc.
Protection, insulator, sole and solid tyre etc..TPU property has than rubber more between plastics and rubber
High intensity, more more preferable than plastics pliability and cold resistance, the raw material that PVC is used as drinking-water pipe can be substituted.But drink
Water pipe requires higher for the combination property of material.Drinking-water pipe not only to have with TPU good flexibility and cold resistance so as to
Bending, again with enough intensity to resist external impacts, and the contradictory part of above-mentioned performance, it tends to be difficult to balance.In addition,
Drinking-water pipe should also have good hydrolytic resistance and anti-microbial property with TPU, ensure the safety of drinking water.
Therefore, the structure and performance of TPU materials how are designed, drinking-water pipe can be used for, is that this area urgently solves
Certainly the problem of.
The content of the invention
In view of the deficienciess of the prior art, it is an object of the invention to provide a kind of TPU materials available for drinking-water pipe
Material and preparation method thereof.TPU materials provided by the invention not only have higher intensity, resistance to tearing energy and pliability, and
Also there is good cold tolerance and anti-microbial property.
To use following technical scheme up to this purpose, the present invention：
On the one hand, the present invention provides a kind of TPU materials available for drinking-water pipe, according to the mass fraction including the following raw material
Component：
30-50 parts diisocyanate, 50-70 parts PPG, 5-20 parts chitosan quaternary ammonium salt, 10-20 parts chain extender,
10-20 parts vulcanizing agent and 0.5-2 part catalyst.
The present invention improves the compliance of polyurethane molecular chain using flexible chitosan quaternary ammonium salt, improves its cold tolerance；
Recycle vulcanizing agent to vulcanize system, chitosan quaternary ammonium salt and polyurethane is formed interpenetrating networks, make up flexible chain intensity
The shortcomings that insufficient, improve tensile strength and tearing strength.In addition, loose chitosan quaternary ammonium salt network can ensure that material has
Good elasticity, and chitosan quaternary ammonium salt also has certain antibacterial action.Matched by said components under specific ratio
Close, higher intensity, resistance to tearing, pliability, good cold tolerance and antibiotic property are had concurrently so as to enable obtained TPU materials
Energy, meet the performance requirement of drinking-water pipe.
In the present invention, the mass fraction of the diisocyanate can be 30 parts, 32 parts, 33 parts, 35 parts, 36 parts, 38 parts,
40 parts, 42 parts, 43 parts, 45 parts, 46 parts, 48 parts or 50 parts etc..
The mass fraction of the PPG can be 50 parts, 52 parts, 53 parts, 55 parts, 56 parts, 58 parts, 60 parts, 62
Part, 63 parts, 65 parts, 66 parts, 68 parts or 70 parts etc..
The mass fraction of the chitosan quaternary ammonium salt can be 5 parts, 6 parts, 8 parts, 10 parts, 12 parts, 13 parts, 15 parts, 16 parts,
18 parts or 20 parts etc..
The mass fraction of the chain extender can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18
Part, 19 parts or 20 parts etc..
The mass fraction of the vulcanizing agent can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18
Part, 19 parts or 20 parts etc..
The mass fraction of the catalyst can be 0.5 part, 0.6 part, 0.8 part, 1 part, 1.2 parts, 1.5 parts, 1.8 parts or 2
Part etc..
As the preferred technical solution of the present invention, the TPU materials include the following raw material component according to the mass fraction：
35-45 parts diisocyanate, 55-65 parts PPG, 10-15 parts chitosan quaternary ammonium salt, 15-20 part chain extensions
Agent, 10-20 parts vulcanizing agent and 0.5-2 part catalyst.
As the preferred technical solution of the present invention, the diisocyanate is aliphatic diisocyanate.
Aliphatic diisocyanate is favorably improved the flexibility of TPU materials, the only not certain poison of aromatic diisocyanate
Property, drinking water is polluted, and for easily causing TPU materials really up to the mark in the present invention, cold resistance is deteriorated.
Preferably, the aliphatic diisocyanate be selected from hexamethylene diisocyanate, IPDI,
Cyclohexyl diisocyanate, cyclohexanedimethyleterephthalate diisocyanate or one kind in dicyclohexyl methyl hydride diisocyanate or extremely
Few two kinds combination.
As the preferred technical solution of the present invention, the number-average molecular weight of the PPG is 3000-5000；Such as can
To be 3000,3200,3500,3800,4000,4200,4500,4800 or 5000 etc..
For the present invention, the molecular weight of PPG is too low, and the Chain Flexibility deficiency of formation, TPU materials resist cold
Property decline；Its molecular weight is too high, easily causes the strength of materials insufficient.
Preferably, one kind in polyethylene glycol, polypropylene glycol or polytetrahydrofuran diol of the PPG or
At least two combination.
As the preferred technical solution of the present invention, the number-average molecular weight of the chitosan quaternary ammonium salt is 5-15 ten thousand；Such as can
To be 50,000,60,000,70,000,80,000,90,000,100,000,110,000,120,000,130,000,140,000 or 150,000 etc..
Preferably, the chain extender by 20-30wt% (such as 20wt%, 21wt%, 22wt%, 23wt%, 24wt%,
25wt%, 26wt%, 27wt%, 28wt%, 29wt% or 30wt% etc.) trimethylolpropane and 70-80wt% (such as
70wt%, 71wt%, 72wt%, 73wt%, 74wt%, 75wt%, 76wt%, 77wt%, 78wt%, 79wt% or 80wt%
Deng) small molecule glycol composition.
Preferably, the small molecule glycol is selected from ethylene glycol, 1,3-PD, BDO, 1,5-PD or 1,
One kind or at least two combination in 6- hexylene glycols.
As the preferred technical solution of the present invention, the vulcanizing agent is the combination of sodium glycero-phosphate and anhydride curing agent.
Preferably, the vulcanizing agent by 15-30wt% (such as 15wt%, 16wt%, 17wt%, 18wt%, 19wt%,
20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt% or 30wt%
Deng) sodium glycero-phosphate and 70-85wt% (such as 70wt%, 71wt%, 72wt%, 73wt%, 74wt%, 75wt%,
76wt%, 77wt%, 78wt%, 79wt%, 80wt%, 81wt%, 82wt%, 83wt%, 84wt% or 85wt% etc.) acid
Anhydride curing agents form.
Sodium glycero-phosphate can make chitosan quaternary ammonium salt quickly form crosslinking, but insecure, the phosphoglycerol of this crosslinking
Sodium dosage excessively easily causes the intensity of material to decline；But the reactivity of anhydride curing agent and chitosan quaternary ammonium salt is relatively low,
If the dosage of sodium glycero-phosphate is very few, the intensity deficiency of material is also resulted in.
Preferably, the anhydride curing agent is HHPA and/or methyl hexahydrophthalic anhydride.
As the preferred technical solution of the present invention, the catalyst is dibutyl tin laurate and/or stannous octoate.
On the other hand, the present invention provides a kind of preparation method of above-mentioned TPU materials, comprises the following steps：
(1) PPG and chitosan quaternary ammonium salt are stirred and be dehydrated by formula；
(2) mixture that step (1) obtains is mixed with diisocyanate, reaction generation prepolymer I；
(3) the polyurethane prepolymer I is mixed with chain extender, vulcanizing agent and catalyst, reaction generation prepolymer II；
(4) the prepolymer II is cured, obtains the TPU materials.
It should be noted that the viscosity of chitosan quaternary ammonium salt is larger, if it is not well mixed with PPG,
Easily cause PPG to be embedded, react insufficient, material bulk property heterogeneity.
As the preferred technical solution of the present invention, the operation in step (1)-step (3) is to carry out under vacuum.
Preferably, the vacuum of the vacuum condition is -0.9~-0.95MPa.
Preferably, the speed stirred described in step (1) is 200-500r/min, such as can be 200r/min, 250r/
Min, 300r/min, 350r/min, 400r/min, 450r/min or 500r/min etc.；Time is 0.5-1h, such as can be
0.5h, 0.6h, 0.7h, 0.8h, 0.9h or 1h etc..
Preferably, the temperature reacted described in step (2) is 60-75 DEG C, for example, can be 60 DEG C, 62 DEG C, 63 DEG C, 65
DEG C, 66 DEG C, 68 DEG C, 70 DEG C, 72 DEG C, 73 DEG C or 75 DEG C etc.；Time is 1-2h, for example, can be 1h, 1.2h, 1.5h, 1.6h,
1.8h or 2h etc..
Preferably, the method mixed described in step (3) is：In 800-1000r/min (such as 800r/min, 820r/
Min, 850r/min, 880r/min, 900r/min, 920r/min, 950r/min, 980r/min or 1000r/min etc.) speed
Lower stirring 10-15s (such as 10s, 11s, 12s, 13s, 14s or 15s etc.).
Preferably, the temperature reacted described in step (3) is 80-90 DEG C, for example, can be 80 DEG C, 81 DEG C, 82 DEG C, 83
DEG C, 84 DEG C, 85 DEG C, 86 DEG C, 87 DEG C, 88 DEG C, 89 DEG C or 90 DEG C etc.；Time is 3-5h, such as can be 3h, 3.5h, 4h, 4.5h
Or 5h etc..
Preferably, the temperature cured described in step (4) is 130-150 DEG C, for example, can be 130 DEG C, 132 DEG C, 133
DEG C, 135 DEG C, 136 DEG C, 138 DEG C, 140 DEG C, 142 DEG C, 143 DEG C, 145 DEG C, 146 DEG C, 148 DEG C or 150 DEG C etc.；Time is 3-6h,
Such as can be 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h etc..
Curing in step (4) is polymerisation is fully carried out, and the process crosslinked.Due to anhydride curing agent
Activity is relatively low, it is therefore desirable to higher temperature.
As the preferred technical solution of the present invention, the preparation method comprises the following steps：
(1) it is -0.9~-0.95MPa, stir speed (S.S.) in vacuum by PPG and chitosan quaternary ammonium salt by formula
To be stirred under conditions of 200-500r/min and being dehydrated 0.5-1h；
(2) mixture that step (1) obtains being mixed with diisocyanate, holding vacuum is -0.9~-0.95MPa,
1-2h, generation prepolymer I are reacted at 60-75 DEG C；
(3) by the polyurethane prepolymer I and chain extender, vulcanizing agent and catalyst under 800-1000r/min speed
10-15s is stirred, holding vacuum is -0.9~-0.95MPa, and 3-5h, generation prepolymer II are reacted at 80-90 DEG C；
(4) the prepolymer II is cured into 3-6h at 130-150 DEG C, obtains the TPU materials.
Compared with prior art, the invention has the advantages that：
The present invention coordinates vulcanizing agent to form interpenetrating networks using flexible chitosan quaternary ammonium salt, can reduce the firm of strand
Property, and can ensure molecule interchain adhesion, each component cooperate, so as to make obtained TPU materials have concurrently higher intensity,
Resistance to tearing energy, pliability, good cold tolerance and anti-microbial property.
The hardness of TPU materials provided by the invention is 85-90, tensile strength 50-55MPa, elongation at break 380-
460%, tearing strength 90-100kN/m；After -45 DEG C handle 24h, tensile strength incrementss≤7%, elongation at break subtracts
On a small quantity≤30%, there is good cold resistance, meet the performance requirement of drinking-water pipe.
Embodiment
Technical scheme is further illustrated below by specific embodiment.Those skilled in the art should be bright
, the embodiment be only to aid in understand the present invention, be not construed as to the present invention concrete restriction.
Embodiment 1
A kind of TPU materials available for drinking-water pipe, according to the mass fraction, its preparing raw material includes：
30 parts of hexamethylene diisocyanates, 70 parts of polyethylene glycol (molecular weight 5000), 20 parts of chitosan quaternary ammonium salt (molecules
Measure 15 ten thousand), 10 parts of chain extenders, 20 parts of vulcanizing agents and 0.5 part of dibutyl tin laurate；
Wherein, chain extender is made up of 2 parts of trimethylolpropanes and 8 parts of ethylene glycol；
Vulcanizing agent is made up of 6 parts of sodium glycero-phosphates and 14 parts of HHPAs.
The preparation method of above-mentioned TPU materials is as follows：
(1) it is -0.9MPa, stir speed (S.S.) 200r/ in vacuum by PPG and chitosan quaternary ammonium salt by formula
It is stirred under conditions of min and is dehydrated 1h；
(2) mixture that step (1) obtains is mixed with diisocyanate, holding vacuum is -0.9MPa, at 60 DEG C
React 2h, generation prepolymer I；
(3) above-mentioned polyurethane prepolymer I and chain extender, vulcanizing agent and catalyst are stirred under 800r/min speed mixed
15s is closed, holding vacuum is -0.9MPa, and 5h, generation prepolymer II are reacted at 80 DEG C；
(4) above-mentioned prepolymer II is cured into 6h at 130 DEG C, obtains above-mentioned TPU materials.
Embodiment 2
A kind of TPU materials available for drinking-water pipe, according to the mass fraction, its preparing raw material includes：
50 parts of IPDIs, 50 parts of polypropylene glycols (molecular weight 3000), 5 parts of chitosan quaternary ammonium salt (molecules
Measure 5 ten thousand), 20 parts of chain extenders, 10 parts of vulcanizing agents and 2 parts of stannous octoates；
Wherein, chain extender is made up of 5 parts of trimethylolpropanes and 15 parts of BDOs；
Vulcanizing agent is made up of 1.5 parts of sodium glycero-phosphates and 8.5 parts of methyl hexahydrophthalic anhydrides.
The preparation method of above-mentioned TPU materials is as follows：
(1) it is -0.95MPa, stir speed (S.S.) 500r/ in vacuum by PPG and chitosan quaternary ammonium salt by formula
It is stirred under conditions of min and is dehydrated 0.5h；
(2) mixture for obtaining step (1) is stirred 10s with diisocyanate under 1000r/min speed, protects
It is -0.95MPa to hold vacuum, and 1h, generation prepolymer I are reacted at 75 DEG C；
(3) above-mentioned polyurethane prepolymer I is mixed with chain extender, vulcanizing agent and catalyst, keep vacuum for-
0.95MPa, 3h, generation prepolymer II are reacted at 90 DEG C；
(4) above-mentioned prepolymer II is cured into 3h at 150 DEG C, obtains above-mentioned TPU materials.
Embodiment 3
A kind of TPU materials available for drinking-water pipe, according to the mass fraction, its preparing raw material includes：
33 parts of cyclohexyl diisocyanates, 67 parts of polytetrahydrofuran diols (molecular weight 4000), 8 parts of chitosan quaternary ammonium salts
(molecular weight 80,000), 12 parts of chain extenders, 15 parts of vulcanizing agents and 1 part of dibutyl tin laurate；
Wherein, chain extender is by 3 parts of trimethylolpropanes and 9 parts of 1,6- hexylene glycols compositions；
Vulcanizing agent is made up of 3 parts of sodium glycero-phosphates and 12 parts of methyl hexahydrophthalic anhydrides.
The preparation method of above-mentioned TPU materials is as follows：
(1) it is -0.9MPa, stir speed (S.S.) 300r/ in vacuum by PPG and chitosan quaternary ammonium salt by formula
It is stirred under conditions of min and is dehydrated 1h；
(2) mixture that step (1) obtains is mixed with diisocyanate, holding vacuum is -0.9MPa, at 65 DEG C
React 1.5h, generation prepolymer I；
(3) above-mentioned polyurethane prepolymer I and chain extender, vulcanizing agent and catalyst are stirred under 900r/min speed mixed
12s is closed, holding vacuum is -0.9MPa, and 4h, generation prepolymer II are reacted at 85 DEG C；
(4) above-mentioned prepolymer II is cured into 5h at 140 DEG C, obtains above-mentioned TPU materials.
Embodiment 4
A kind of TPU materials available for drinking-water pipe, according to the mass fraction, its preparing raw material includes：
35 parts of cyclohexanedimethyleterephthalate diisocyanate, 65 parts of polyethylene glycol (molecular weight 5000), 10 parts of chitosan quaternary ammoniums
Salt (molecular weight 80,000), 18 parts of chain extenders, 12 parts of vulcanizing agents and 1.5 parts of stannous octoates；
Wherein, chain extender is made up of 4 parts of trimethylolpropanes and 14 parts of 1,5-PDs；
Vulcanizing agent is made up of 2.5 parts of sodium glycero-phosphates and 9.5 parts of HHPAs.
The preparation method of above-mentioned TPU materials is as follows：
(1) it is -0.9MPa, stir speed (S.S.) 400r/ in vacuum by PPG and chitosan quaternary ammonium salt by formula
It is stirred under conditions of min and is dehydrated 0.5h；
(2) mixture that step (1) obtains is mixed with diisocyanate, holding vacuum is -0.9MPa, at 70 DEG C
React 1.5h, generation prepolymer I；
(3) above-mentioned polyurethane prepolymer I and chain extender, vulcanizing agent and catalyst are stirred under 900r/min speed mixed
12s is closed, holding vacuum is -0.9MPa, and 4.5h, generation prepolymer II are reacted at 80 DEG C；
(4) above-mentioned prepolymer II is cured into 4.5h at 135 DEG C, obtains above-mentioned TPU materials.
Embodiment 5
A kind of TPU materials available for drinking-water pipe, according to the mass fraction, its preparing raw material includes：
40 parts of dicyclohexyl methyl hydride diisocyanates, 60 parts of polypropylene glycols (molecular weight 4000), 13 parts of chitosan quaternary ammonium salts
(molecular weight 120,000), 16 parts of chain extenders, 15 parts of vulcanizing agents and 1 part of dibutyl tin laurate；
Wherein, chain extender is made up of 4 parts of trimethylolpropanes and 12 parts of 1,3-PDs；
Vulcanizing agent is made up of 4.5 parts of sodium glycero-phosphates and 10.5 parts of HHPAs.
The preparation method of above-mentioned TPU materials is as follows：
(1) it is -0.95MPa, stir speed (S.S.) 300r/ in vacuum by PPG and chitosan quaternary ammonium salt by formula
It is stirred under conditions of min and is dehydrated 0.5h；
(2) mixture that step (1) obtains is mixed with diisocyanate, holding vacuum is -0.95MPa, at 60 DEG C
Lower reaction 2h, generation prepolymer I；
(3) above-mentioned polyurethane prepolymer I and chain extender, vulcanizing agent and catalyst are stirred under 900r/min speed mixed
12s is closed, holding vacuum is -0.95MPa, and 3h, generation prepolymer II are reacted at 90 DEG C；
(4) above-mentioned prepolymer II is cured into 6h at 130 DEG C, obtains above-mentioned TPU materials.
Embodiment 6
A kind of TPU materials available for drinking-water pipe, according to the mass fraction, its preparing raw material includes：
45 parts of IPDIs, 55 parts of polytetrahydrofuran diols (molecular weight 3000), 12 parts of chitosan quaternary ammoniums
Salt (molecular weight 100,000), 18 parts of chain extenders, 15 parts of vulcanizing agents and 0.8 part of stannous octoate；
Wherein, chain extender is made up of 5 parts of trimethylolpropanes and 13 parts of BDOs；
Vulcanizing agent is made up of 3 parts of sodium glycero-phosphates and 12 parts of methyl hexahydrophthalic anhydrides.
The preparation method of above-mentioned TPU materials is as follows：
(1) it is -0.95MPa, stir speed (S.S.) 400r/ in vacuum by PPG and chitosan quaternary ammonium salt by formula
It is stirred under conditions of min and is dehydrated 1h；
(2) mixture that step (1) obtains is mixed with diisocyanate, holding vacuum is -0.95MPa, at 75 DEG C
Lower reaction 1h, generation prepolymer I；
(3) above-mentioned polyurethane prepolymer I and chain extender, vulcanizing agent and catalyst are stirred under 900r/min speed mixed
12s is closed, holding vacuum is -0.95MPa, and 4h, generation prepolymer II are reacted at 85 DEG C；
(4) above-mentioned prepolymer II is cured into 4h at 140 DEG C, obtains above-mentioned TPU materials.
Comparative example 1
Difference with embodiment 1 is that the dosage of chitosan quaternary ammonium salt is 0, other raw materials, dosage and preparation process and reality
It is identical to apply example.
Comparative example 2
Difference with embodiment 1 is that diisocyanate is toluene di-isocyanate(TDI), other raw materials, dosage and preparation process
It is identical with embodiment.
Comparative example 3
Difference with embodiment 1 is that the molecular weight of polyethylene glycol is 2000, other raw materials, dosage and preparation process and reality
It is identical to apply example.
Comparative example 4
Difference with embodiment 1 is that the molecular weight of chitosan quaternary ammonium salt is 200,000, other raw materials, dosage and preparation process
It is identical with embodiment.
Comparative example 5
Difference with embodiment 1 is that vulcanizing agent is HHPA, other raw materials, dosage and preparation process and embodiment phase
Together.
Comparative example 6
Difference with embodiment 1 is that vulcanizing agent is sodium glycero-phosphate, other raw materials, dosage and preparation process and embodiment
It is identical.
The performance of above-described embodiment 1-6 and comparative example 1-6 TPU materials provided is tested, testing standard and result
It is as shown in table 1 below.
As shown in Table 1, when not adding chitosan quaternary ammonium salt or using aromatic diisocyanate, can cause
The tensile strength and tearing strength of TPU materials decline, and cold resistance is deteriorated；When the molecular weight of PPG is too low, TPU soft segments
Rigidity increase, Materials Fracture elongation decline, and cold resistance is deteriorated；When the molecular weight of chitosan quaternary ammonium salt is too high, system viscosity
It is larger, it is difficult to which that reflection is abundant, causes the hardness, tensile strength and tearing strength of TPU materials to be decreased obviously；When only with single
Vulcanizing agent when, TPU is difficult to form interpenetrating networks, and the hardness and intensity of material decline to a great extent.Only when each raw material is specific
Ratio under when cooperating, can just obtain the good TPU materials for drinking-water pipe of combination property.
Applicant states, the foregoing is only the embodiment of the present invention, but protection scope of the present invention not office
It is limited to this, person of ordinary skill in the field is it will be clearly understood that any belong to those skilled in the art and taken off in the present invention
In the technical scope of dew, the change or replacement that can readily occur in, all fall within protection scope of the present invention and it is open within the scope of.
Claims (10)
1. a kind of TPU materials available for drinking-water pipe, it is characterised in that the TPU materials include as follows according to the mass fraction
Raw material components：
30-50 parts diisocyanate, 50-70 parts PPG, 5-20 parts chitosan quaternary ammonium salt, 10-20 parts chain extender, 10-
20 parts of vulcanizing agents and 0.5-2 part catalyst.
2. TPU materials according to claim 1, it is characterised in that the TPU materials include following former according to the mass fraction
Expect component：
35-45 parts diisocyanate, 55-65 parts PPG, 10-15 parts chitosan quaternary ammonium salt, 15-20 parts chain extender, 10-
20 parts of vulcanizing agents and 0.5-2 part catalyst.
3. TPU materials according to claim 1 or 2, it is characterised in that the diisocyanate is the isocyanic acid of aliphatic two
Ester；
Preferably, the aliphatic diisocyanate is selected from hexamethylene diisocyanate, IPDI, hexamethylene
Group diisocyanate, cyclohexanedimethyleterephthalate diisocyanate or one kind in dicyclohexyl methyl hydride diisocyanate or at least two
The combination of kind.
4. the TPU materials according to any one of claim 1-3, it is characterised in that the number of the PPG is divided equally
Son amount is 3000-5000；
Preferably, one kind in polyethylene glycol, polypropylene glycol or polytetrahydrofuran diol of the PPG or at least
Two kinds of combination.
5. the TPU materials according to any one of claim 1-4, it is characterised in that the number of the chitosan quaternary ammonium salt is equal
Molecular weight is 5-15 ten thousand；
Preferably, the chain extender is made up of 20-30wt% trimethylolpropane and 70-80wt% small molecule glycol；
Preferably, the small molecule glycol be selected from ethylene glycol, 1,3-PD, BDO, 1,5-PD or 1,6- oneself
One kind or at least two combination in glycol.
6. the TPU materials according to any one of claim 1-5, it is characterised in that the vulcanizing agent is sodium glycero-phosphate
With the combination of anhydride curing agent；
Preferably, the vulcanizing agent is made up of 15-30wt% sodium glycero-phosphate and 70-85wt% anhydride curing agent；
Preferably, the anhydride curing agent is HHPA and/or methyl hexahydrophthalic anhydride.
7. the TPU materials according to any one of claim 1-6, it is characterised in that the catalyst is tin dilaurate two
Butyl tin and/or stannous octoate.
8. the preparation method of the TPU materials according to any one of claim 1-7, it is characterised in that the preparation method
Comprise the following steps：
(1) PPG and chitosan quaternary ammonium salt are stirred and be dehydrated by formula；
(2) mixture that step (1) obtains is mixed with diisocyanate, reaction generation prepolymer I；
(3) the polyurethane prepolymer I is mixed with chain extender, vulcanizing agent and catalyst, reaction generation prepolymer II；
(4) the prepolymer II is cured, obtains the TPU materials.
9. preparation method according to claim 7, it is characterised in that the operation in step (1)-step (3) is in vacuum
Under the conditions of carry out；
Preferably, the vacuum of the vacuum condition is -0.9~-0.95MPa；
Preferably, the speed stirred described in step (1) is 200-500r/min, time 0.5-1h；
Preferably, the temperature reacted described in step (2) is 60-75 DEG C, time 1-2h；
Preferably, the method mixed described in step (3) is：10-15s is stirred under 800-1000r/min speed；
Preferably, the temperature reacted described in step (3) is 80-90 DEG C, time 3-5h；
Preferably, the temperature cured described in step (4) is 130-150 DEG C, time 3-6h.
10. preparation method according to claim 8 or claim 9, it is characterised in that the preparation method comprises the following steps：
(1) by formula by PPG and chitosan quaternary ammonium salt vacuum be -0.9~-0.95MPa, stir speed (S.S.) be
It is stirred under conditions of 200-500r/min and is dehydrated 0.5-1h；
(2) mixture that step (1) obtains is mixed with diisocyanate, holding vacuum is -0.9~-0.95MPa, in 60-
1-2h, generation prepolymer I are reacted at 75 DEG C；
(3) the polyurethane prepolymer I is stirred under 800-1000r/min speed with chain extender, vulcanizing agent and catalyst
10-15s is mixed, holding vacuum is -0.9~-0.95MPa, and 3-5h, generation prepolymer II are reacted at 80-90 DEG C；
(4) the prepolymer II is cured into 3-6h at 130-150 DEG C, obtains the TPU materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711077686.4A CN107828037A (en) | 2017-11-06 | 2017-11-06 | A kind of TPU materials available for drinking-water pipe and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711077686.4A CN107828037A (en) | 2017-11-06 | 2017-11-06 | A kind of TPU materials available for drinking-water pipe and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107828037A true CN107828037A (en) | 2018-03-23 |
Family
ID=61654500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711077686.4A Pending CN107828037A (en) | 2017-11-06 | 2017-11-06 | A kind of TPU materials available for drinking-water pipe and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107828037A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112011025A (en) * | 2020-07-14 | 2020-12-01 | 安徽嘉明新材料科技有限公司 | Natural polymer modified polyurethane and preparation method thereof |
| CN113652160A (en) * | 2021-08-17 | 2021-11-16 | 武汉佳顺源防腐科技有限公司 | Polyurethane coating and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583853A (en) * | 2004-06-01 | 2005-02-23 | 武汉大学 | Elastic material containing nitrated casing glycan, its preparing method and use thereof |
| CN101664562A (en) * | 2009-09-30 | 2010-03-10 | 都本立 | Wound repair hydrogel material and preparation method thereof |
| CN102658072A (en) * | 2012-05-22 | 2012-09-12 | 江南大学 | Preparation method for monodispersed chitosan hollow microspheres |
| CN102911335A (en) * | 2012-10-19 | 2013-02-06 | 奥斯汀新材料（张家港）有限公司 | Preparation method of natural macromolecular modified thermoplastic polyurethane elastomer |
| CN104707164A (en) * | 2015-03-31 | 2015-06-17 | 中国人民解放军军事医学科学院基础医学研究所 | Composite chitosan hydrogel dressing as well as preparation method and applications thereof |
| CN106012567A (en) * | 2016-07-28 | 2016-10-12 | 东莞市雄林新材料科技股份有限公司 | Environment-friendly antibacterial TPU (thermoplastic polyurethanes) synthetic leather and preparation method thereof |
| CN106220814A (en) * | 2016-07-21 | 2016-12-14 | 淄博德信联邦化学工业有限公司 | Polyurethane elastomer antifreezing faucet and preparation method thereof |
| CN106893067A (en) * | 2017-03-15 | 2017-06-27 | 东莞市雄林新材料科技股份有限公司 | A kind of low deformation antibacterial polyurethane automobile shock damping, buffering pad and preparation method thereof |
-
2017
- 2017-11-06 CN CN201711077686.4A patent/CN107828037A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583853A (en) * | 2004-06-01 | 2005-02-23 | 武汉大学 | Elastic material containing nitrated casing glycan, its preparing method and use thereof |
| CN101664562A (en) * | 2009-09-30 | 2010-03-10 | 都本立 | Wound repair hydrogel material and preparation method thereof |
| CN102658072A (en) * | 2012-05-22 | 2012-09-12 | 江南大学 | Preparation method for monodispersed chitosan hollow microspheres |
| CN102911335A (en) * | 2012-10-19 | 2013-02-06 | 奥斯汀新材料（张家港）有限公司 | Preparation method of natural macromolecular modified thermoplastic polyurethane elastomer |
| CN104707164A (en) * | 2015-03-31 | 2015-06-17 | 中国人民解放军军事医学科学院基础医学研究所 | Composite chitosan hydrogel dressing as well as preparation method and applications thereof |
| CN106220814A (en) * | 2016-07-21 | 2016-12-14 | 淄博德信联邦化学工业有限公司 | Polyurethane elastomer antifreezing faucet and preparation method thereof |
| CN106012567A (en) * | 2016-07-28 | 2016-10-12 | 东莞市雄林新材料科技股份有限公司 | Environment-friendly antibacterial TPU (thermoplastic polyurethanes) synthetic leather and preparation method thereof |
| CN106893067A (en) * | 2017-03-15 | 2017-06-27 | 东莞市雄林新材料科技股份有限公司 | A kind of low deformation antibacterial polyurethane automobile shock damping, buffering pad and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| SHU-HUEI YU等: "Miscibility, mechanical characteristic and platelet adhesion of 6-O-carboxymethylchitosan/polyurethane semi-IPN membranes", 《JOURNAL OF MEMBRANE SCIENCE》 * |
| 刘振儒等: "水溶性壳聚糖季铵盐的抗菌性能", 《青岛科技大学学报(自然科学版)》 * |
| 强涛涛: "《合成革化学品》", 31 July 2016, 中国轻工业出版社 * |
| 徐霞等: "壳聚糖季铵盐衍生物的合成及其抗菌活性", 《信阳师范学院学报(自然科学版)》 * |
| 蔡照胜等: "季铵化壳聚糖及其絮凝六价铬性能的研究", 《工业用水与废水》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112011025A (en) * | 2020-07-14 | 2020-12-01 | 安徽嘉明新材料科技有限公司 | Natural polymer modified polyurethane and preparation method thereof |
| CN112011025B (en) * | 2020-07-14 | 2022-01-14 | 安徽嘉明新材料科技有限公司 | Natural polymer modified polyurethane and preparation method thereof |
| CN113652160A (en) * | 2021-08-17 | 2021-11-16 | 武汉佳顺源防腐科技有限公司 | Polyurethane coating and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104292414B (en) | A kind of organic-silicon-modified both sexes aqueous polyurethane emulsion and preparation method thereof | |
| CN109554101A (en) | A kind of polyurethane water-proof paint | |
| CN107141441A (en) | A kind of low-refraction high transparency TPUE and preparation method thereof | |
| CN110156952B (en) | Dual-curable polyurethane toughened resin and preparation method and application thereof | |
| CN106634547B (en) | A kind of one-component exposed conveying appliance acrylic acid modified polyurethane water-repellent paint and preparation method | |
| CN101629061A (en) | Monocomponent moisture cure urethanes adhesive | |
| CN104559734A (en) | Double-component chemical-reaction thixotropic polyurethane waterproof paint and preparation method thereof | |
| CN106380829A (en) | Waterborne polyurethane gloves slurry, preparation method thereof, and waterborne polyurethane gloves prepared from the same | |
| CN107118321A (en) | One kind has high obstructing performance TPUE and preparation method thereof | |
| CN105693982B (en) | A kind of polyurethane plastic runway second component and preparation method thereof and application based on polyurethane degraded product preparation | |
| KR101427122B1 (en) | Coating material for hand application | |
| CN106753174A (en) | Adhesives of composite pavement and preparation method thereof, water-proof crack-resistant layer | |
| CN106833481A (en) | Environment-friendly type organosilicon modified polyether seal glue and preparation method thereof | |
| CN114181605B (en) | Single-component water-based polyurethane waterproof coating and preparation method thereof | |
| CN104987489A (en) | Highly-wear-resistant, low-temperature-resistant, folding-resistant, hydrolysis-resistant polyurethane surfacing resin | |
| CN107828037A (en) | A kind of TPU materials available for drinking-water pipe and preparation method thereof | |
| CN105238256B (en) | A kind of allyl ether is modified single-component polyurethane water-proof paint and preparation method thereof | |
| JP2008297338A (en) | Two-pack type urethane composition for application of urethane rubber-based coated film waterproofing material, and method for applying urethane rubber-based coated film waterproofing material by using the same | |
| CN113980563B (en) | Method for preparing one-component semi-polyurea waterproof coating composition and one-component semi-polyurea waterproof coating composition | |
| CN109096945B (en) | Tackifier applied to silicone sealant and preparation method thereof | |
| CN116023626B (en) | Hydrolysis-resistant high-solid-content closed polyurethane resin composition and preparation method thereof | |
| CN115785850B (en) | Adhesion promoter, preparation method and application thereof, and waterproof adhesive single-component polyurethane sealant, and preparation method and application thereof | |
| CN108102058B (en) | Single-component solvent-free self-leveling polyurethane elastomer | |
| KR20150025992A (en) | Urethane waterproofing material using slag | |
| CN113943544A (en) | Water-based environment-friendly adhesive and preparation method thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180323 |
|
| RJ01 | Rejection of invention patent application after publication |