CN109942784A - A kind of linear thermoplastic's polyurethane Anchor Agent and preparation method thereof - Google Patents
A kind of linear thermoplastic's polyurethane Anchor Agent and preparation method thereof Download PDFInfo
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- CN109942784A CN109942784A CN201810836613.7A CN201810836613A CN109942784A CN 109942784 A CN109942784 A CN 109942784A CN 201810836613 A CN201810836613 A CN 201810836613A CN 109942784 A CN109942784 A CN 109942784A
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Abstract
The present invention provides a kind of linear thermoplastic's polyurethane Anchor Agent and preparation method thereof, and wherein the Anchor Agent is in terms of mass fraction, including following component: isocyanates: 4-6.1 parts, polyether polyol: 10-12 parts, chain extender: 0.8-1 parts, end-capping reagent: 0.1-1 parts, catalyst: 0.01-0.1 parts.The Anchor Agent ANA and PVC that the present invention is prepared dissolves each other, firmness change rate decline 44%, eduction rate decline 72% at the retention rate of elongation at break improve 285% times, -10 DEG C when Anchor Agent ANA dosage is to 60 parts, -30 DEG C.Anchor Agent ANA with DOTP composite elasticizer compared with pure DOTP plasticizer, -30 DEG C of firmness change rates be its 24%, -10 DEG C of migration precipitation rates be only its 5%.
Description
Technical field
The present invention relates to field of material technology more particularly to a kind of linear thermoplastic's polyurethane Anchor Agent and its preparation sides
Method.
Background technique
Polyvinyl chloride (PVC) is a kind of widely used general-purpose plastics, has excellent mechanical property, is domestic and international refrigerator
Sealing strip main material claims ratio 90% in domestic refrigerator sealing strip according to the insiders, and dosage is more than 30,000 tons.PVC cryogenic property
Difference, temperature sensitive, as temperature declines, hardness rises and flexibility decrease is obvious, and is used for a long time, and plasticizer is close
Effect decline is sealed, shows on refrigerator to be exactly to generate gap between sealing strip and cabinet, there is phenomena such as condensation, frosting in refrigerator,
Power consumption increases, or even causes compressor twenty four hours continuous service, affects the service life of compressor.
Summary of the invention
It is an object of the invention to solve the problems of the above-mentioned prior art, provide a kind of low to improve refrigerator sealing strip
The problems such as warm hardness rises, flexibility decrease and long-time plasticizer, it is good to make a kind of resistance to low temperature by oneself, compatible with PVC
Good, the linear thermoplastic's polyurethane Anchor Agent ANA of resistance to migration precipitation of property.
A kind of linear thermoplastic's polyurethane Anchor Agent, raw material is in terms of mass fraction, comprising: isocyanates: 4-6.1 parts,
Dimethylformamide: 20 parts, polyether polyol: 10-12 parts, chain extender: 0.8-1 parts, end-capping reagent: 0.1-1 parts, catalyst:
0.01-0.1 parts.
Further, linear thermoplastic's polyurethane Anchor Agent as described above, the isocyanates are that isophorone two is different
Cyanate.
Further, linear thermoplastic's polyurethane Anchor Agent as described above, the polyether polyol are molecular weight 1100
Polyethylene glycol propylene glycol-polyethylene glycol copolymer.
Further, linear thermoplastic's polyurethane Anchor Agent as described above, the chain extender are 1,4-butanediol, sealing end
Agent is ethyl alcohol, and catalyst is that dibutyl tin dilaurate is used in compounding with stannous octoate.
Further, linear thermoplastic's polyurethane Anchor Agent as described above, the dibutyl tin dilaurate and octanoic acid
The mass ratio of stannous is 3:1.
A kind of preparation method of linear thermoplastic's polyurethane Anchor Agent, comprising the following steps:
Step 1: polyether polyol is no less than 1h in 120 DEG C ± 10 DEG C, not less than the vacuum dehydration time under -0.08MPa,
Then anhydrous grade dimethylformamide is added after being cooled to 70 DEG C ± 10 DEG C, not to moisture and oxygen, is added
Isocyanates is stirred with 100~150 revs/min of revolving speed, and 2h, 0.1~0.15MPa of pressure are reacted at 75~85 DEG C, is prepared
Anchor Agent prepolymer out；
Step 2: chain extender and catalyst being added in Xiang Suoshu Anchor Agent prepolymer, is stirred with 100-150 revs/min of revolving speed
It mixes, 2-3h is reacted at 105-115 DEG C, pressure 0.1-0.15MPa prepares uncapped Anchor Agent；
Step 3: end-capping reagent is added into uncapped Anchor Agent, is stirred with 100~150 revs/min of revolving speed, in 65~85
DEG C, 4~5h is reacted under 0.15~0.3MPa pressure；Stirring is settled out applied to soft PVC modification in anhydrous ether
Anchor Agent.
The thermoplastic polyurethane (Anchor Agent ANA) for the intermediate molecular weight that the present invention is finally prepared has following superiority
Can:
A, with excellent low temperature flexibility and anti-yellowing property；
B, with excellent low temperature flexibility and anti-hydrolytic performance；
c、Mn=15000~18000, Mw/Mn=1.3~1.5, molecular weight is low, can be easier relative to conventional polyurethanes
Be interspersed in flexible PVC, be easier to distribution compatibility it is good, the processing temperature of conventional polyurethanes, cannot be soft at 180 DEG C or so
PVC process uses, and Anchor Agent processing temperature is low, can match with flexible PVC processing temperature, and hardness is extremely low to be made
For plasticizer use, the hardness of flexible PVC is reduced, improves elasticity.
Detailed description of the invention
Fig. 1 be Anchor Agent, isocyanates, polyether polyol infrared spectrum；
Fig. 2 is the Tan Delta curve of Anchor Agent ANA；
Fig. 3 is the DSC temperature profile of Anchor Agent ANA；
Fig. 4 is flexible PVC at 25 DEG C, -10 DEG C, -30 DEG C of elongation at break；
Fig. 5 is for flexible PVC in -10 DEG C and -30 DEG C relative to 25 DEG C of reserved elongation at break；
Fig. 6 is the hardness figure of flexible PVC system at different temperatures；
Fig. 7 is for flexible PVC system relative to the firmness change rate figure at 25 DEG C at -10 DEG C and -30 DEG C；
Fig. 8 is the firmness change rate figure of pure DOTP system and DOTP/ Anchor Agent compound system；
Fig. 9 is the storage modulus figure of flexible PVC system；
Figure 10 is that the Tan Delta of flexible PVC system schemes；
Figure 11 is the T of flexible PVC systemgTheoretical value and actual value figure；
Figure 12 is that the SEM of flexible PVC schemes；
Figure 13 is EDS element (N, Cl) distribution map of 10000 times of amplification in 3# flexible PVC brittle failure face；
Figure 14 is the mobility figure of flexible PVC system at different temperatures；
Figure 15 is the migration and variation rate figure of pure DOTP system and DOTP/ Anchor Agent compound system.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, the technical solution below in the present invention carries out clear
Chu is fully described by, it is clear that described embodiments are some of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Though the low polyurethane liquid plasticizer of molecular weight has speedup effect, cryogenic property can be improved, similarly had
Migration precipitation problem.The big thermoplastic polyurethane (Anchor Agent ANA) of molecular weight is the modified elastomer of PVC, contains phenyl ring mostly
Or be aliphatic, processing temperature is high, and poor performance at low temperatures, no speedup effect is poor, is not suitable for processing low flexible PVC as temperature
Plasticizer uses, and is only applicable to the toughening modifying of hard PVC.And the thermoplastic polyurethane of intermediate molecular weight prepared by the present invention
Hydrogen bond is formed between (Anchor Agent ANA) Anchor Agent, with polyvinyl chloride (PVC) and plasticizer agent, since polyurethane contains soft and hard segments,
Hardness can form hydrogen bond with PVC and plasticizer, prevent plasticizer, and soft segment provides flexibility, improves the low temperature properties of PVC
Energy.
The Anchor Agent ANA and PVC that the present invention is prepared dissolves each other, and fracture is stretched when Anchor Agent ANA dosage is to 60 parts, -30 DEG C
Firmness change rate decline 44%, eduction rate decline 72% at the retention rate of long rate improve 285% times, -10 DEG C.Anchor Agent ANA
With DOTP composite elasticizer compared with pure DOTP plasticizer, -30 DEG C of firmness change rates be its 24%, -10 DEG C of migration precipitation rates are only
For its 5%.
The present invention provides a kind of linear thermoplastic's polyurethane Anchor Agent, in terms of mass fraction, including following component: isocyanic acid
Ester: 4-6.1 parts, dimethylformamide: 20 parts, polyether polyol: 10-12 parts, chain extender: 0.8-1 parts, end-capping reagent: 0.1-1
Part, catalyst: 0.01-0.1 parts.Wherein, the isocyanates is isoflurane chalcone diisocyanate.
The polyether polyol is 1100 polyethylene glycol propylene glycol of molecular weight-polyethylene glycol copolymer.
The chain extender is 1,4-butanediol, and end-capping reagent is ethyl alcohol, and catalyst is that dibutyl tin dilaurate and octanoic acid are sub-
Tin is used in compounding.
The present invention also provides a kind of preparation methods of linear thermoplastic's polyurethane Anchor Agent, comprising the following steps:
Step 1: 10~12 parts by weight polyether polyol being added in reaction kettle, in 120 DEG C or so, not less than -0.08MPa
The lower vacuum dehydration time will be no less than 1h, then be cooled to 70 DEG C or so.The anhydrous grade dimethylformamide of 20 parts by weight is added, to anti-
It answers and is passed through nitrogen in kettle and clears away moisture and oxygen etc. as far as possible, take the isocyanates of 4~6.1 parts by weight that reaction kettle is added, with 100~
150 revs/min of revolving speed stirring, reacts 2h, 0.1~0.15MPa of pressure prepares the pre-polymerization of Anchor Agent at 75~85 DEG C
Object.
Step 2: to 0.8-1 parts of chain extenders and 0.01-0.1 parts of catalyst are added among reaction kettle, with 100-150 revs/min
The revolving speed of clock stirs, and 2-3h is reacted at 105-115 DEG C, pressure 0.1-0.15MPa prepares uncapped Anchor Agent；
Step 3: 0.1~1 part of end-capping reagent is added, is stirred with 100~150 revs/min of revolving speed, in 65~85 DEG C,
4~5h is reacted under 0.15~0.3MPa pressure；Stirring is settled out the anchor modified applied to soft PVC in anhydrous ether
Gu agent is transferred in special container and stores.
Experimental example 1:
The structural analysis of the fourier-transform infrared (FTIR) of thermoplastic polyurethane Anchor Agent ANA
Whether it is Anchor Agent ANA for verifying synthetic product, its structure is studied with FTIR, Fig. 1 is IPDI, PEG-
The infared spectrum of the Anchor Agent ANA of PPG-PEG synthesis.As shown in Figure 1, PEG-PPG-PEG is-an OH at 3474cm-1
Stretching vibration peak, IPDI's is-N=C=O a characteristic absorption peak at 2259cm-1, after reaction generates Anchor Agent ANA,
The stretching vibration peak of appearance-NH at 3334cm-1, the bending vibration of appearance-NH at 1533cm-1 are-C=O at 1719cm-1
Stretching vibration, show that the characteristic group-NHCOO- of Anchor Agent ANA is generated, the absorption peak at 3474cm-1 and 2259cm-1 is complete
Portion disappears, and shows fully reacting, has synthesized Anchor Agent ANA Anchor Agent.
Experimental example 2:
The osmogels chromatography (GPC) of Anchor Agent ANA is tested
Show to be successfully prepared required Anchor Agent ANA oligomer " Anchor Agent " by gel permeation chromatography test.Mn=
18814, MW=28430, Mw/Mn=1.51, this Anchor Agent ANA " Anchor Agent " molecular weight is appropriate, and molecular weight distribution is relatively narrow.
Experimental example 3:
The dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) of Anchor Agent ANA is analyzed
Fig. 2 is the Tan Delta curve of Anchor Agent ANA, as shown in Figure 2 the glass transition temperature of homemade Anchor Agent ANA
(Tg) is spent at -30.3 DEG C or so, being eliminated by Fig. 3 can only see Tg at -29.6 DEG C in the DSC heating and temperature lowering curve of thermal history,
And have no peak crystallization and melting peak, thus speculate that self-control Anchor Agent ANA may not be crystallized.PEG-PPG-PEG structure is irregular to be made
Inhibit the crystallization of Anchor Agent ANA.The low crystallization of synthesis or non crystalline structure and the Anchor Agent ANA for possessing low Tg, have excellent
Cryogenic property.
Experimental example 4:
The mechanical property and hardness and dynamic mechanical properties (DMA) of flexible PVC are analyzed
Reserved elongation at break=l1/l0× 100%---- (1)
L in formula (1)1It is -10 DEG C and -30 DEG C of corresponding elongation at break；l0It is the elongation at break of 25 DEG C of materials.
Fig. 4 is flexible PVC at 25 DEG C, -10 DEG C, and -30 DEG C of elongation at break, Fig. 5 is soft PV in -10 DEG C and -30 DEG C
Relative to 25 DEG C of reserved elongation at break (formula 1), by Fig. 4, Fig. 5 it is found that the elongation at break of room temperature and cryogenic material with
Anchor Agent ANA dosage increase and increase, with Anchor Agent ANA dosage increase, at -10 DEG C the retention rate of elongation at break by
70.1% increases to 78.8%, and the retention rate of elongation at break increases to 36.5% by 12.8% at -30 DEG C, material at low temperature bullet
Property dramatically increases.Elasticity increases obvious at -30 DEG C, and retention rate increases nearly 285%.
Firmness change rate=h1/h0× 100%-1---- (2)
Formula (2) h1It is -10 DEG C and -30 DEG C of corresponding hardness；h0It is 25 DEG C of hardness.
Found out by Fig. 6-Fig. 8, as Anchor Agent ANA dosage increases, the hardness of room temperature and cryogenic material reduces, Anchor Agent
ANA has plasticization effect, can be used as plasticizer use, with Anchor Agent ANA dosage increase at -10 DEG C firmness change rate from
9% is reduced to 5%, reduces by 44%, and firmness change rate is reduced to 7.6% from 11.3% at -30 DEG C, declines 33%, Anchor Agent
ANA significantly improves the temperature sensitivity of flexible PVC.DOTP/ANA=50/60 composite elasticizer and simple DOTP/ANA=
110/0 compares, and DOTP/ANA=110/0 has lower hardness, and DOTP plasticizing efficiency is higher than self-control Anchor Agent ANA " Anchor Agent ",
But declining its firmness change rate at -10 DEG C with temperature is 16.7%, more reaches 31.4% in -30 DEG C of firmness change rates, -10 DEG C
At -30 DEG C, the firmness change rate of DOTP/ANA=50/6 is only 31% He of the firmness change rate of DOTP/ANA=110/0
24%.It can be seen that the low-temperature toughness that the addition of Anchor Agent ANA can greatly improve flexible PVC increases phenomenon.
Fig. 9 and Figure 10 is respectively the storage modulu and glass transition temperature (T of flexible PVCg).It can be seen from Fig.6
In TgWhen following, storage modulus is gradually decreased with Anchor Agent ANA dosage increase, shows that the rigidity of flexible PVC reduces, flexibility increases
Add, cryogenic property improves.Fig.7 is the Tan Delta of flexible PVC, and polymer compatibility is better, component TgCloser to[9],
Only one T of all flexible PVCs in figureg, it was demonstrated that PVC and Anchor Agent ANA have good compatibility, as Anchor Agent ANA is used
Amount increases, TgIt reduces, from the T of DOTP/ANA=50/0g=30.7 DEG C of T for being reduced to DOTP/ANA=50/60g=6.7 DEG C, under
24 DEG C of drop.
Increase with Anchor Agent ANA " Anchor Agent ", the T of flexible PVCgIt reduces, thus it is higher in performance Anchor Agent ANA content,
Elongation at break is higher, and hardness is lower, and performance Anchor Agent ANA content is higher at low temperature, and reserved elongation at break is got over
Greatly, firmness change rate is smaller.Anchor Agent ANA strand has soft ether section, can still move at low temperature, reduce material
Rigidity, so hardness rising is smaller.Reserved elongation at break is bigger, and the smaller efficiency for sealing material of firmness change rate has
It improves, reduces because firmness change bring endangers, directly have energy-saving effect for fields such as refrigerators.
Fox etc. has found compound Fox formula between the Tg and each component mass fraction of Compatibilized blends.
1/Tg=WA/Tga+WB/Tgb---- (3)
W in formula (3)A、WBThe mass fraction of respectively PVC and Anchor Agent ANA.
By Figure 11, it is known that increase the T of sample with Anchor Agent ANA dosagegWith theoretical value TgIt matches, Fox equation establishment condition
For only one glass transition temperature of mixture, and to meet theoretical value, it is possible thereby to backstepping returns, PVC and self-control Anchor Agent ANA
" Anchor Agent " compatibility is fabulous, can dissolve each other.
Experimental example 5:
Flexible PVC scanning electron microscope (SEM) analysis
Figure 12 is 1#, 3#, 4#, and 5# amplifies 1000 times of brittle failure Surface scan electron microscope, the results show that increasing with Ana, surface
Irregularities become larger, and protrusion is obvious, until 5# protrusion is maximum, illustrate that toughness is significantly increased, and have no obvious layering and aggregation, show two
Person's compatibility is good.
Wherein, the 1#, 3#, 4#, 5# respectively represent flexible PVC system at 0,30,45,60 parts of Anchor Agent of addition.
Experimental example 6:
Figure 13 is EDS element (N, Cl) distribution map of 10000 times of amplification in the brittle failure face 3#, by EDS elemental analysis, finds anchor
Gu agent ANA (N element) is uniformly distributed in PVC (Cl element), Anchor Agent ANA clustering phenomena, self-control Anchor Agent is further proved
ANA " Anchor Agent " dissolves each other with PVC.
Experimental example 7:
Flexible PVC migration precipitation experiment
P=(X0-Xa)/X0× 100%-------- (4)
P is mobility/‰ in formula (4)；X0For the quality before processing, XaFor sample through 25 DEG C with after -10 DEG C of constant temperature 72h
Quality.
Increased by Figure 14, Figure 15 are visible with Anchor Agent ANA, eduction rate reduces, and -10 DEG C of eduction rate is apparently higher than 25 DEG C
Eduction rate.And as Anchor Agent ANA increases, the two gap is gradually reduced, until the close Anchor Agent ANA dosage of 45 parts of eduction rates increases
When adding to 60 parts, decline 50% and 72% respectively in the eduction rate of 25 DEG C and -10 DEG C.DOTP/ANA=50/60 it is compound with it is simple
DOTP/ANA=110/0 is compared, and the migration precipitation rate of DOTP/ANA=110/0 is 12.8 ‰ with -10 DEG C for 7.8 ‰ at 25 DEG C.
DOTP/ANA=50/60 only has the 7% and 5% of DOTP/ANA=110/0 migration precipitation rate in the eduction rate of 25 DEG C and -10 DEG C,
It can be seen that Anchor Agent ANA " Anchor Agent ", which is added, can greatly improve the precipitation problem of flexible PVC.Due to making Anchor Agent by oneself
ANA, DOTP and PVC three form hydrogen bond, active force enhancing, and DOTP eduction rate reduces.Low migration precipitation rate is conducive to protection ring
Border and food grade materials to be used for, has higher development prospect, for a long time using can also reduce because plasticizer bring is hard
Degree rises, and increases sealing performance, reaches energy-saving effect.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (6)
1. a kind of linear thermoplastic's polyurethane Anchor Agent, which is characterized in that its original is in terms of mass fraction, comprising: isocyanates: 4-
6.1 parts, dimethylformamide: 20 parts, polyether polyol: 10-12 parts, chain extender: 0.8-1 parts, end-capping reagent: 0.1-1 parts, catalysis
Agent: 0.01-0.1 parts.
2. linear thermoplastic's polyurethane Anchor Agent according to claim 1, which is characterized in that the isocyanates is different fluorine
That ketone diisocyanate.
3. linear thermoplastic's polyurethane Anchor Agent according to claim 1, which is characterized in that the polyether polyol is point
Son amount 1100 polyethylene glycol propylene glycol-polyethylene glycol copolymer.
4. linear thermoplastic's polyurethane Anchor Agent according to claim 1, which is characterized in that the chain extender is Isosorbide-5-Nitrae-fourth
Glycol, end-capping reagent are ethyl alcohol, and catalyst is that dibutyl tin dilaurate is used in compounding with stannous octoate.
5. linear thermoplastic's polyurethane Anchor Agent according to claim 4, which is characterized in that the di lauric dibutyl
The mass ratio of tin and stannous octoate is 3:1.
6. a kind of preparation method of linear thermoplastic's polyurethane Anchor Agent, which comprises the following steps:
Step 1: polyether polyol being no less than 1h in 120 DEG C ± 10 DEG C, not less than the vacuum dehydration time under -0.08MPa, then
Anhydrous grade dimethylformamide is added after being cooled to 70 DEG C ± 10 DEG C, not to moisture and oxygen, isocyanide is added
Acid esters is stirred with 100~150 revs/min of revolving speed, 2h is reacted at 75~85 DEG C, 0.1~0.15MPa of pressure prepares anchor
Gu agent prepolymer；
Step 2: chain extender and catalyst are added in Xiang Suoshu Anchor Agent prepolymer, is stirred with 100-150 revs/min of revolving speed,
2-3h is reacted at 105-115 DEG C, pressure 0.1-0.15MPa prepares uncapped Anchor Agent；
Step 3: end-capping reagent is added into uncapped Anchor Agent, is stirred with 100~150 revs/min of revolving speed, in 65~85 DEG C,
4~5h is reacted under 0.15~0.3MPa pressure；Stirring is settled out the anchor modified applied to soft PVC in anhydrous ether
Gu agent.
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| CN111157395A (en) * | 2020-01-09 | 2020-05-15 | 南京林业大学 | Method for quantitatively analyzing interaction between starch and plasticizer in starch plastic |
| CN111157395B (en) * | 2020-01-09 | 2023-06-06 | 南京林业大学 | Method for quantitatively analyzing interaction of starch and plasticizer in starch plastic |
| CN115059722A (en) * | 2022-05-31 | 2022-09-16 | 江苏省纺织研究所股份有限公司 | Impact-resistant self-repairing multilayer composite material and preparation method thereof |
| CN115059722B (en) * | 2022-05-31 | 2023-09-29 | 江苏省纺织研究所股份有限公司 | Impact-resistant self-repairing multilayer composite material and preparation method thereof |
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