CN109942784B - Linear thermoplastic polyurethane anchoring agent and preparation method thereof - Google Patents
Linear thermoplastic polyurethane anchoring agent and preparation method thereof Download PDFInfo
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Abstract
The invention provides a linear thermoplastic polyurethane anchoring agent and a preparation method thereof, wherein the anchoring agent comprises the following components in parts by mass: isocyanate: 4-6.1 parts of polyether polyol: 10-12 parts of a chain extender: 0.8-1 part of end capping agent: 0.1-1 part, catalyst: 0.01-0.1 portion. The anchoring agent ANA prepared by the invention is mutually soluble with PVC, the dosage of the anchoring agent ANA is 60 parts, the retention rate of the elongation at break is improved by 285% times at minus 30 ℃, the change rate of the hardness is reduced by 44% at minus 10 ℃, and the precipitation rate is reduced by 72%. Compared with pure DOTP plasticizer, the ANA and DOTP composite plasticizer of the anchoring agent has the hardness change rate of 24 percent at the temperature of-30 ℃ and the migration separation rate of 5 percent at the temperature of-10 ℃.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a linear thermoplastic polyurethane anchoring agent and a preparation method thereof.
Background
Polyvinyl chloride (PVC) is widely used general plastic, has excellent mechanical property, is a main material of refrigerator sealing strips at home and abroad, and is called 90 percent of the refrigerator sealing strips at home by the people in the industry, and the dosage of the PVC exceeds 3 ten thousand tons. PVC low temperature performance is poor, and is sensitive to the temperature, and along with the temperature decline, hardness rises and elasticity descends obviously, and long-term the use, the plasticizer is appeared, and sealed effect descends, shows on the refrigerator just produce the gap between sealing strip and the box, and the refrigerator appears condensation, phenomenon such as frost, and power consumption increases, causes the compressor twenty four hours to last the operation even, has influenced the life of compressor.
Disclosure of Invention
The invention aims to solve the defects of the prior art, and provides a linear thermoplastic polyurethane anchoring agent ANA which has good low temperature resistance, good compatibility with PVC and migration and precipitation resistance and is used for improving the problems of low-temperature hardness increase, elasticity reduction, long-time plasticizer precipitation and the like of a refrigerator sealing strip.
A linear thermoplastic polyurethane anchoring agent comprises the following raw materials in parts by mass: isocyanate: 4-6.1 parts of dimethylformamide: 20 parts of polyether polyol: 10-12 parts of a chain extender: 0.8-1 part of end capping agent: 0.1-1 part, catalyst: 0.01-0.1 portion.
Further, the linear thermoplastic polyurethane anchoring agent as described above, wherein the isocyanate is isophorone diisocyanate.
Further, as the linear thermoplastic polyurethane anchoring agent described above, the polyether polyol is a copolymer of polyethylene glycol-polypropylene glycol-polyethylene glycol having a molecular weight of 1100.
Further, according to the linear thermoplastic polyurethane anchoring agent, the chain extender is 1, 4-butanediol, the end capping agent is ethanol, and the catalyst is dibutyltin dilaurate and stannous octoate which are compounded for use.
Further, in the linear thermoplastic polyurethane anchoring agent as described above, the mass ratio of the dibutyltin dilaurate to the stannous octoate is 3: 1.
A preparation method of a linear thermoplastic polyurethane anchoring agent comprises the following steps:
step 1: carrying out vacuum dehydration on polyether polyol at 120 +/-10 ℃ and under the pressure of not less than-0.08 MPa for not less than 1h, then cooling to 70 +/-10 ℃, adding anhydrous grade dimethyl formamide, adding isocyanate under the conditions of no water and oxygen, stirring at the rotating speed of 100-150 r/min, reacting at 75-85 ℃ for 2h and under the pressure of 0.1-0.15MPa, and preparing an anchoring agent prepolymer;
step 2: adding a chain extender and a catalyst into the anchoring agent prepolymer, stirring at the rotating speed of 100-;
and step 3: adding the end-capping agent into the non-end-capped anchoring agent, stirring at the rotating speed of 100-150 rpm, and reacting for 4-5 hours at the temperature of 65-85 ℃ and under the pressure of 0.15-0.3 MPa; stirring and precipitating in anhydrous ether to obtain the anchoring agent applied to the modification of the soft polyvinyl chloride.
The thermoplastic polyurethane (anchoring agent ANA) with medium molecular weight finally prepared by the invention has the following excellent properties:
a. has excellent low-temperature flexibility and yellowing resistance;
b. has excellent low-temperature flexibility and hydrolysis resistance;
c、Mn＝15000～18000，Mw/Mnthe soft PVC anchoring agent has the advantages that the soft PVC anchoring agent has low molecular weight, can be easily inserted into soft PVC compared with common polyurethane, is easy to distribute and has good compatibility, the processing temperature of the common polyurethane is about 180 ℃, the common polyurethane cannot be used in the processing process of the soft PVC, the processing temperature of the anchoring agent is low, the anchoring agent can be matched with the processing temperature of the soft PVC, the hardness is extremely low, the soft PVC anchoring agent can be used as a plasticizer, the hardness is reduced, and the elasticity is improved.
Drawings
FIG. 1 is an infrared spectrum of an anchoring agent, isocyanate, polyether polyol;
FIG. 2 is a Tan Delta curve for the anchoring agent ANA;
FIG. 3 is a DSC temperature profile of the anchoring agent ANA;
FIG. 4 shows the elongation at break of soft PVC at 25 ℃, -10 ℃, -30 ℃;
FIG. 5 is the elongation at break retention of flexible PVC at-10 ℃ and-30 ℃ versus 25 ℃;
FIG.6 is a graph of hardness of soft PVC systems at different temperatures;
FIG.7 is a graph of the rate of change of hardness at-10 ℃ and-30 ℃ versus 25 ℃ for a soft PVC system;
FIG. 8 is a graph of hardness change for a pure DOTP system and a DOTP/anchoring agent combination system;
FIG. 9 is a graph of the storage modulus of a flexible PVC system;
FIG. 10 is a Tan Delta chart for a flexible PVC system;
FIG. 11 is T of a flexible PVC systemgA graph of theoretical and actual values of;
FIG. 12 is an SEM image of soft PVC;
FIG. 13 is a graph of EDS element (N, Cl) distribution at 10000 times magnification within a 3# soft PVC brittle section;
FIG. 14 is a graph of mobility for flexible PVC systems at different temperatures;
FIG. 15 is a graph of mobility change for pure DOTP systems and DOTP/anchoring agent complex systems.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described below clearly and completely, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The polyurethane liquid plasticizer having a low molecular weight has a speed-increasing effect and can improve low-temperature performance, but also has a migration and precipitation problem. The thermoplastic polyurethane (anchoring agent ANA) with large molecular weight is a PVC modified elastomer, mostly contains benzene rings or is aliphatic, has high processing temperature, poor low-temperature performance and no poor acceleration effect, is not suitable for being used as a plasticizer of soft PVC with low temperature processing, and is only suitable for toughening and modifying hard PVC. The thermoplastic polyurethane (anchoring agent ANA) anchoring agent with medium molecular weight prepared by the invention forms hydrogen bonds with polyvinyl chloride (PVC) and the plasticizer, and because the polyurethane contains soft and hard segments, the hardness can form the hydrogen bonds with the PVC and the plasticizer, the plasticizer is prevented from being separated out, the soft segments provide flexibility, and the low-temperature performance of the PVC is improved.
The anchoring agent ANA prepared by the invention is mutually soluble with PVC, the dosage of the anchoring agent ANA is 60 parts, the retention rate of the elongation at break is improved by 285% times at minus 30 ℃, the change rate of the hardness is reduced by 44% at minus 10 ℃, and the precipitation rate is reduced by 72%. Compared with pure DOTP plasticizer, the ANA and DOTP composite plasticizer of the anchoring agent has the hardness change rate of 24 percent at the temperature of-30 ℃ and the migration separation rate of 5 percent at the temperature of-10 ℃.
The invention provides a linear thermoplastic polyurethane anchoring agent, which comprises the following components in parts by mass: isocyanate: 4-6.1 parts of dimethylformamide: 20 parts of polyether polyol: 10-12 parts of a chain extender: 0.8-1 part of end capping agent: 0.1-1 part, catalyst: 0.01-0.1 portion. Wherein the isocyanate is isophorone diisocyanate.
The polyether polyol is a copolymer of polyethylene glycol-polypropylene glycol-polyethylene glycol with the molecular weight of 1100.
The chain extender is 1, 4-butanediol, the end capping agent is ethanol, and the catalyst is dibutyltin dilaurate and stannous octoate which are compounded for use.
The invention also provides a preparation method of the linear thermoplastic polyurethane anchoring agent, which comprises the following steps:
step 1: adding 10-12 parts by weight of polyether polyol into a reaction kettle, dehydrating at about 120 ℃ and not less than-0.08 MPa in vacuum for not less than 1h, and then cooling to about 70 ℃. Adding 20 parts by weight of anhydrous dimethylformamide, introducing nitrogen into the reaction kettle to sweep away water, oxygen and the like as much as possible, adding 4-6.1 parts by weight of isocyanate into the reaction kettle, stirring at the rotating speed of 100-150 rpm, reacting at 75-85 ℃ for 2 hours under the pressure of 0.1-0.15MPa, and preparing the prepolymer of the anchoring agent.
Step 2: adding 0.8-1 part of chain extender and 0.01-0.1 part of catalyst into a reaction kettle, stirring at the rotating speed of 100-;
and step 3: adding 0.1-1 part of end-capping reagent, stirring at a rotating speed of 100-150 rpm, and reacting at 65-85 ℃ and under a pressure of 0.15-0.3 MPa for 4-5 h; stirring and precipitating in anhydrous ether to obtain the anchoring agent for modifying soft polyvinyl chloride, and transferring into a special container for storage.
Experimental example 1:
structural analysis of Fourier Transform Infrared (FTIR) of thermoplastic polyurethane Anchor ANA
To verify whether the synthesized product is the ANA anchoring agent, the structure of the ANA anchoring agent is studied by FTIR, and FIG. 1 is an infrared spectrum of the ANA anchoring agent synthesized by IPDI and PEG-PPG-PEG. As can be seen from fig. 1, PEG-PPG-PEG has a stretching vibration peak of — OH at 3474cm-1, IPDI has a characteristic absorption peak of — N ═ C ═ O at 2259cm-1, after the reaction generates the anchor ANA, a stretching vibration peak of-NH appears at 3334cm-1, a bending vibration of-NH appears at 1533cm-1, and a stretching vibration of-C ═ O at 1719cm-1 indicates that the characteristic group of the anchor ANA, i.e., NHCOO-, is generated, and the absorption peaks at 3474cm-1 and 2259cm-1 all disappear, indicating that the reaction is complete and the anchor ANA is synthesized.
Experimental example 2:
permeability gel chromatography (GPC) testing of Anchorage agent ANA
Gel permeation chromatography tests show that the ANA oligomer serving as the required anchoring agent is successfully prepared. 18814 Mn, 28430 MW and 1.51 Mw/Mn, and the ANA as one kind of anchoring agent has proper molecular weight and narrow molecular weight distribution.
Experimental example 3:
dynamic Mechanical Analysis (DMA) and Differential Scanning Calorimetry (DSC) analysis of the anchoring agent ANA
FIG. 2 is a Tan Delta curve of the anchoring agent ANA, and it can be seen from FIG. 2 that the glass transition temperature (Tg) of the home-made anchoring agent ANA is around-30.3 deg.C, and only Tg of-29.6 deg.C can be seen on the DSC temperature rise and fall curve of FIG. 3 eliminating the heat history, and no crystallization peak and melting peak are seen, so it is presumed that the home-made anchoring agent ANA may not be crystallized. The PEG-PPG-PEG structural irregularities inhibit the crystallization of the anchoring agent ANA. The synthesized anchoring agent ANA with low crystalline or amorphous structure and low Tg has excellent low-temperature performance.
Experimental example 4:
mechanical Properties and hardness and dynamic mechanical Properties (DMA) analysis of Soft PVC
Retention of elongation at break ═ l1/l0×100％---- (1)
In the formula (1) < i >1Is the elongation at break corresponding to-10 ℃ and-30 ℃; l0Is the elongation at break of the material at 25 ℃.
Fig. 4 shows the elongation at break of the flexible PVC at 25 ℃, -10 ℃, -30 ℃, and fig. 5 shows the retention of elongation at break of the flexible PV at-10 ℃ and-30 ℃ relative to the elongation at break at 25 ℃ (equation 1), and it can be seen from fig. 4 and fig. 5 that the elongation at break of the normal and low temperature material increases with the increase of the amount of the anchoring agent ANA, the retention of elongation at break at-10 ℃ increases from 70.1% to 78.8% with the increase of the amount of the anchoring agent ANA, and the retention of elongation at break at-30 ℃ increases from 12.8% to 36.5%, and the elasticity at low temperature of the material significantly increases. The elasticity is obviously increased at the temperature of minus 30 ℃, and the retention rate is increased by nearly 285 percent.
Hardness change rate h1/h0×100％-1---- (2)
Formula (2) h1Hardness corresponding to-10 ℃ and-30 ℃; h is0Is a hardness of 25 ℃.
As seen from FIGS. 6 to 8, as the amount of the ANA used as the anchoring agent is increased, the hardness of the material at normal temperature and low temperature is reduced, the ANA used as the anchoring agent has a plasticizing effect and can be used as a plasticizer, the hardness change rate at-10 ℃ is reduced from 9% to 5% and 44% and the hardness change rate at-30 ℃ is reduced from 11.3% to 7.6% and 33%, and the ANA used as the anchoring agent remarkably improves the temperature sensitivity of the soft PVC. Compared with the simple DOTP/ANA (110/0), the DOTP/ANA (50/60) compound plasticizer has lower hardness than the DOTP/ANA (110/0), the DOTP plasticizing efficiency is higher than that of a home-made anchoring agent ANA (anchoring agent), but the hardness change rate of the DOTP/ANA (50/6) is 16.7 percent at minus 10 ℃ and more 31.4 percent at minus 30 ℃, and the hardness change rate of the DOTP/ANA (50/6) is only 31 percent and 24 percent of that of the DOTP/ANA (110/0) at minus 10 ℃ and minus 30 ℃. Therefore, the phenomenon of low-temperature hardness increase of the soft PVC can be greatly improved by adding the anchoring agent ANA.
FIG. 9 and FIG. 10 are soft respectivelyStorage modulus and glass transition temperature (T) of PVCg). From FIG.6, it can be seen that at TgWhen the soft PVC material is used, the storage modulus is gradually reduced along with the increase of the using amount of the anchoring agent ANA, which shows that the rigidity of the soft PVC material is reduced, the flexibility is increased, and the low-temperature performance is improved. Fin.7 is Tan Delta of Soft PVC, the better the compatibility of the polymer, the component TgThe closer to[9]In the figure, all soft PVC have only one TgThe compatibility between PVC and the ANA is proved to be good, and T is increased along with the increase of the using amount of the ANAgDecrease from DOTP/ANA 50/0TgT reduction to DOTP/ANA 50/60 at 30.7 ℃g6.7 ℃ and a drop of 24 ℃.
T of soft PVC with increase of ANA (Anchorage agent)gAnd so the higher the content of ANA as an anchor agent is expressed, the higher the elongation at break is, and the lower the hardness is, and the higher the content of ANA as an anchor agent is expressed at a low temperature, the higher the retention of elongation at break is, and the lower the change in hardness is. The molecular chain of the ANA anchoring agent is provided with a soft ether segment, and the ANA anchoring agent can still move at low temperature, so that the rigidity of the material is reduced, and the hardness is increased less. The retention rate of elongation at break is larger, the hardness change rate is smaller, the efficiency of the sealing material is improved, the harm caused by hardness change is reduced, and the energy-saving effect is directly realized in the fields of refrigerators and the like.
Fox et al found the Tg of the compatible blends and the composite Fox equation between the mass fractions of the components.
1/Tg＝WA/Tga+WB/Tgb---- (3)
W in formula (3)A、WBRespectively the mass fractions of PVC and the anchoring agent ANA.
From FIG. 11, it can be seen that T of the sample is increased with the amount of ANA as the anchoring agentgAnd theoretical value TgThe conditions of the Fox equation are that the mixture has only one glass transition temperature and the theoretical value is satisfied, so that the mixture can be reversely pushed back, and PVC and the self-made anchoring agent ANA (Artificial Natural organic acid) are extremely good in compatibility and mutually soluble.
Experimental example 5:
scanning Electron Microscopy (SEM) analysis of Soft PVC
Fig. 12 is a brittle fracture surface scanning electron microscope image magnified 1000 times by 1#, 3#, 4#, and 5#, and the result shows that as Ana increases, the surface unevenness becomes larger, the protrusions become obvious, and the protrusions become the largest in 5#, which indicates that the toughness is greatly increased, and no obvious layering and aggregation are seen, indicating that the compatibility between the two is good.
Wherein, the 1#, 3#, 4#, 5# respectively represent soft PVC system when 0, 30,45,60 parts of anchoring agent are added.
Experimental example 6:
fig. 13 is a graph of EDS element (N, Cl) distribution at 10000 times magnification in # 3 brittle section, and by EDS element analysis, it was found that the anchor ANA (N element) was uniformly distributed in PVC (Cl element), and the anchor ANA aggregation phenomenon, further demonstrating that the home-made anchor ANA "anchor" was mutually soluble with PVC.
Experimental example 7:
migration and precipitation experiment of soft PVC
P＝(X0-Xa)/X0×100％-------- (4)
In the formula (4), P is mobility per mill; x0For pre-treatment quality, XaThe mass of the sample is constant temperature of 25 ℃ and-10 ℃ for 72 hours.
As can be seen from FIGS. 14 and 15, the precipitation rate decreased with the increase of ANA, and the precipitation rate at-10 ℃ was significantly higher than that at 25 ℃. And as the ANA of the anchoring agent increases, the difference between the two is gradually reduced until the precipitation rate of 45 parts is similar, and when the using amount of the ANA of the anchoring agent increases to 60 parts, the precipitation rates at 25 ℃ and-10 ℃ are respectively reduced by 50 percent and 72 percent. Compared with the simple DOTP/ANA (110/0), the DOTP/ANA (50/60) compound has the migration separation rate of 110/0 at 25 ℃ of 7.8 thousandths and 12.8 thousandths at-10 ℃. The precipitation rate of DOTP/ANA (50/60) at 25 ℃ and-10 ℃ is only 7% and 5% of the migration precipitation rate of DOTP/ANA (110/0), so that the problem of precipitation of soft PVC can be greatly improved by adding the anchor agent ANA (anchoring agent). As the self-made anchoring agent ANA, DOTP and PVC form hydrogen bonds, the acting force is enhanced, and the precipitation rate of DOTP is reduced. The low migration precipitation rate is beneficial to protecting the environment and being used for food-grade materials, has higher development prospect, can reduce the hardness increase caused by the precipitation of the plasticizer after long-time use, increases the sealing performance and achieves the energy-saving effect.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (6)
1. The linear thermoplastic polyurethane anchoring agent is characterized by comprising the following raw materials in parts by mass: isocyanate: 4-6.1 parts of dimethylformamide: 20 parts of polyether polyol: 10-12 parts of a chain extender: 0.8-1 part of end capping agent: 0.1-1 part, catalyst: 0.01-0.1 part;
M n=15000～18000，M w/M n=1.3～1.5。
2. the linear thermoplastic polyurethane anchoring agent of claim 1, wherein the isocyanate is isophorone diisocyanate.
3. The linear thermoplastic polyurethane anchor according to claim 1, wherein the polyether polyol is a copolymer of polyethylene glycol-polypropylene glycol-polyethylene glycol having a molecular weight of 1100.
4. The linear thermoplastic polyurethane anchoring agent of claim 1, wherein the chain extender is 1, 4-butanediol, the capping agent is ethanol, and the catalyst is dibutyltin dilaurate used in combination with stannous octoate.
5. The linear thermoplastic polyurethane anchor of claim 4, wherein the mass ratio of dibutyltin dilaurate to stannous octoate is 3: 1.
6. A preparation method of a linear thermoplastic polyurethane anchoring agent is characterized by comprising the following steps:
step 1: carrying out vacuum dehydration on polyether polyol at 120 +/-10 ℃ and not less than-0.08 MPa for not less than 1h, then cooling to 70 +/-10 ℃, adding anhydrous dimethylformamide, adding isocyanate under the condition of no water and oxygen, stirring at the rotating speed of 100-150 r/min, reacting at 75-85 ℃ for 2h and under the pressure of 0.1-0.15MPa, and preparing an anchoring agent prepolymer;
step 2: adding a chain extender and a catalyst into the anchoring agent prepolymer, stirring at the rotating speed of 100-;
and step 3: adding the end-capping agent into the non-end-capped anchoring agent, stirring at the rotating speed of 100-150 rpm, and reacting for 4-5 hours at the temperature of 65-85 ℃ and under the pressure of 0.15-0.3 MPa; stirring and precipitating in anhydrous ether to obtain an anchoring agent applied to the modification of the soft polyvinyl chloride;
M n=15000～18000，M w/M n=1.3～1.5。
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