CN104177805B - The blend of carbon dioxide-epoxy propane copolymer and its preparation method - Google Patents
The blend of carbon dioxide-epoxy propane copolymer and its preparation method Download PDFInfo
- Publication number
- CN104177805B CN104177805B CN201410449423.1A CN201410449423A CN104177805B CN 104177805 B CN104177805 B CN 104177805B CN 201410449423 A CN201410449423 A CN 201410449423A CN 104177805 B CN104177805 B CN 104177805B
- Authority
- CN
- China
- Prior art keywords
- carbon dioxide
- formula
- epoxy propane
- propane copolymer
- blend
- 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.)
- Active
Links
Landscapes
- Epoxy Resins (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The blend of carbon dioxide-epoxy propane copolymer provided by the invention, carbon dioxide-base polyurethanes compound and carbon dioxide-epoxy propane copolymer is used to carry out blended, owing to carbonic acid gas based polyurethanes is obtained by the carbon dioxide-epoxy propane copolymer polyvalent alcohol of lower molecular weight and isocyanic ester chain extending reaction, make carbonic acid gas based polyurethanes can have good consistency with carbon dioxide-epoxy propane copolymer, and then improve the interfacial adhesion of blend, stress is effectively transmitted in interface, so that the blend of carbon dioxide-epoxy propane copolymer provided by the invention not only tensile strength and Young's modulus height, and elongation at break is also higher.
Description
Technical field
The present invention relates to polymer modification field, particularly relate to blend and its preparation method of a kind of carbon dioxide-epoxy propane copolymer.
Background technology
Carbon dioxide-epoxy propane copolymer (PPC) is a kind of aliphatic polycarbonate prepared under the effect of catalyzer by carbonic acid gas and propylene oxide, it it is a kind of Full degradation type macromolecular material, the carbon dioxide chemistry being greater than total amount 40wt% can be fixed by PPC in building-up process, and the environmental problem brought for alleviation carbonic acid gas isothermal chamber gas plays active effect; In addition, PPC is with low cost, and has the features such as high transparent, excellent barrier properties for gases and processibility, it is possible to be used in film and wrapping material field, is conducive to the white pollution problems that the conventional plastic such as alleviation polyethylene polypropylene are brought. But PPC molecule presents amorphous state and intermolecular interaction is weak, causes its second-order transition temperature lower, therefore, owing to PPC uses fragility big at low temperatures, poor toughness; And at high temperature poor dimensional stability, intensity is low, and then limits the application of PPC.
In order to widen the Application Areas of PPC, it is necessary to its mechanical property is carried out modification. at present, by physical blending, PPC carrying out modification is one of method of widely using, mainly comprise: the high-molecular weight polymer of PPC and other kinds carries out blended, PPC and other inorganic particulates carry out blended and PPC and other low-molecular weight compound carries out blended, as: (document: the ExpressPolymerLetters2012 such as Fu Qiang, 6 (11), 860-870) in the blended process of PLA/PPC, add a small amount of polyvinyl acetate (PVA) (PVAc), with SEM and DSC and Mechanics Performance Testing, blend is characterized, result display PVAc selective distribution is in PLA phase district and PPC/PLA phase interface, add PVAc and significantly improve PPC/PLA consistency, Shi Xiang district diminishes, interface binding power increases, the blend intensity and the toughness that add PVAc are all big than the blend in proportion not adding PVAc, 70PPC/30PLA/10PVAc tensile strength reaches 28.5MPa, elongation at break reaches 187%, with PP similar mechanical, (the NewChemicalMaterials2012 such as Xu Guang, 40 (3), method disclosed in 63-66), for increasing the interface binding power of starch granules and PPC, prepared at melt blending by the method for reactive modification and starch/PPC composite material adds '-diphenylmethane diisocyanate (MDI), result display adds MDI makes a small amount of PPC be grafted on starch microparticle surfaces, thus improve the consistency changing starch granules and PPC matrix, but owing to grafting efficiency is low, although the tensile strength of blend increases to some extent after adding MDI, elongation at break is still lower than pure PPC. visible, although carbon dioxide-epoxy propane copolymer blending modification method can be increased carbon dioxide-epoxy propane copolymer tensile strength and Young's modulus that prior art provides, but all make its elongation at break reduce, limit the range of application of PPC.
Summary of the invention
In view of this, technical problem to be solved by this invention is providing blend and its preparation method of a kind of carbon dioxide-epoxy propane copolymer, and not only tensile strength and Young's modulus are good for blend provided by the invention, and elongation at break is higher.
The present invention provides the blend of a kind of carbon dioxide-epoxy propane copolymer, in weight fraction, comprising:
The carbonic acid gas based polyurethanes of 2.5��20 weight parts;
The carbon dioxide-epoxy propane copolymer of 80��97.5 weight parts;
The structure of described carbonic acid gas based polyurethanes such as formula shown in I,
Wherein, x is 10%��90%, y is 90%��10%, and x+y=1;
Z is 2��30;
N is 35��100;
R is the structure shown in formula (II), formula (III) or formula (IV),
Wherein, * is link position, and i is the integer of 2��8;
R1 is the structure shown in formula (V), formula (VI), formula (VII), formula (VIII), formula (IX), formula (X), formula (XI) or formula (XII),
Wherein, * is link position, and j is the integer of 1��10.
Preferably, the number-average molecular weight of described carbonic acid gas based polyurethanes is 30000��80000, and molecular weight distributing index is 1.5��3.0.
Preferably, the number-average molecular weight of described carbon dioxide-epoxy propane copolymer is 50000��300000, and molecular weight distributing index is 1.2��4.5.
Present invention also offers the preparation method of the blend of a kind of carbon dioxide-epoxy propane copolymer, comprising:
A) the carbonic acid gas based polyurethanes of 2.5��20 weight parts is mixed with the carbon dioxide-epoxy propane copolymer of 80��97.5 weight parts, obtain mixture;
The structure of described carbonic acid gas based polyurethanes such as formula shown in I,
Wherein, x is 10%��90%, y is 90%��10%, and x+y=1;
Z is 2��30;
N is 35��100;
R is the structure shown in formula (II), formula (III) or formula (IV),
Wherein, * is link position, and i is the integer of 2��8;
R1 is the structure shown in formula (V), formula (VI), formula (VII), formula (VIII), formula (IX), formula (X), formula (XI) or formula (XII),
Wherein, * is link position, and j is the integer of 1��10;
B) by mixture melt blending, the blend of carbon dioxide-epoxy propane copolymer is obtained.
Preferably, the number-average molecular weight of described carbonic acid gas based polyurethanes is 30000��80000, and molecular weight distributing index is 1.5��3.0.
Preferably, the number-average molecular weight of described carbon dioxide-epoxy propane copolymer is 50000��300000, and molecular weight distributing index is 1.2��4.5.
Preferably, the temperature of described melt blending is 120 DEG C��230 DEG C.
Preferably, described carbonic acid gas based polyurethanes is prepared in accordance with the following methods:
By the carbon dioxide-epoxy propane copolymer dibasic alcohol of small-molecular-weight and isocyanic ester hybrid reaction, obtain carbonic acid gas based polyurethanes.
Preferably, the molecular weight of the carbon dioxide-epoxy propane copolymer dibasic alcohol of described small-molecular-weight is 1000��2000, and molecular weight distribution is 1.0��1.5.
Preferably, the carbon dioxide-epoxy propane copolymer dibasic alcohol of described small-molecular-weight and the mass ratio of described isocyanic ester are (1.5��0.7): (1.3��0.8).
Compared with prior art, the blend of carbon dioxide-epoxy propane copolymer provided by the invention, carbon dioxide-base polyurethanes compound and carbon dioxide-epoxy propane copolymer is used to carry out blended, owing to carbonic acid gas based polyurethanes is obtained by the carbon dioxide-epoxy propane copolymer polyvalent alcohol of lower molecular weight and isocyanic ester chain extending reaction, make carbonic acid gas based polyurethanes can have good consistency with carbon dioxide-epoxy propane copolymer, and then improve the interfacial adhesion of blend, stress is effectively transmitted in interface, so that the blend of carbon dioxide-epoxy propane copolymer provided by the invention not only tensile strength and Young's modulus height, and elongation at break is also higher, experimental result shows, the elongation at break of blend provided by the invention is all more than 20%, and tensile strength and non-notched Izod impact strength are all higher than pure PPC.
Present invention also offers the preparation method of the blend of a kind of carbon dioxide-epoxy propane copolymer, undertaken blended by the method for melting after described carbon dioxide-epoxy propane copolymer and carbonic acid gas based polyurethanes are mixed, condition is easy to control, technique is simple, with low cost, it is applicable to suitability for industrialized production.
Accompanying drawing explanation
The infrared spectrogram of the carbonic acid gas based polyurethanes that Fig. 1 provides for the embodiment of the present invention 1;
The infrared spectrogram of the carbonic acid gas based polyurethanes that Fig. 2 provides for the embodiment of the present invention 2.
Embodiment
The present invention provides the blend of a kind of carbon dioxide-epoxy propane copolymer, with weight parts, comprising:
The carbonic acid gas based polyurethanes of 2.5��20 weight parts;
The carbon dioxide-epoxy propane copolymer of 80��97.5 weight parts;
The structure of described carbonic acid gas based polyurethanes such as formula shown in I,
Wherein, x is 10%��90%, y is 90%��10%, and x+y=1;
Z is 2��30;
N is 35��100;
R is the structure shown in formula (II), formula (III) or formula (IV),
Wherein, * is link position, and i is the integer of 2��8;
R1 is the structure shown in formula (V), formula (VI), formula (VII), formula (VIII), formula (IX), formula (X), formula (XI) or formula (XII),
Wherein, * is link position, and j is the integer of 1��10.
According to the present invention, the number-average molecular weight of described carbonic acid gas based polyurethanes is preferably 30000��80000, it is more preferable to be 40000��60000; The molecular weight distributing index of described carbonic acid gas based polyurethanes is preferably 1.5��3.0, it is more preferable to be 1.6��2.0; The number-average molecular weight of described carbon dioxide-epoxy propane copolymer is preferably 50000��300000, it is more preferable to be 1000000��200000; The molecular weight distributing index of described carbon dioxide-epoxy propane copolymer is preferably 1.2��4.5; Described carbonic acid gas based polyurethanes content in the blend is preferably 3��18 weight parts, it is more preferable to be 5��15 weight parts; Described carbon dioxide-epoxy propane copolymer content in the blend is preferably 82��97 weight parts, it is more preferable to be 85��95 weight parts.
In the structure of the formula (I) shown in carbonic acid gas based polyurethanes of the present invention, described i is preferably 4��7, it is more preferable to be 4,5 or 6; Described j is preferably 2��8, it is more preferable to be 3,4,5,6,7; The source of described carbonic acid gas based polyurethanes is not had particular requirement by the present invention, it is preferable that prepare in accordance with the following methods:
By the carbon dioxide-epoxy propane copolymer dibasic alcohol of small-molecular-weight and isocyanic ester hybrid reaction, obtain carbonic acid gas based polyurethanes.
Concrete, the carbon dioxide-epoxy propane copolymer dibasic alcohol of small-molecular-weight and isocyanic ester hybrid reaction, the molecular weight of the carbon dioxide-epoxy propane copolymer dibasic alcohol of described small-molecular-weight is 1000��2000 by the present invention, and molecular weight distribution is 1.0��1.5; Carbonate content in the carbon dioxide-epoxy propane copolymer dibasic alcohol of described small-molecular-weight is preferably 30%, 40%, 50% or 60%; Described isocyanic ester be preferably in tolylene diisocyanate, hexamethylene diisocyanate and diphenylmethanediisocyanate one or more, it is more preferable to be tolylene diisocyanate; The carbon dioxide-epoxy propane copolymer dibasic alcohol of described small-molecular-weight and the mass ratio of described isocyanic ester are (1.5��0.7): (1.3��0.8), the temperature of described hybrid reaction is preferably 100��110 DEG C, and the time of described hybrid reaction is preferably 0.25��1 hour.
Further; better carry out to react; the present invention is preferably before hybrid reaction; first the carbon dioxide-epoxy propane copolymer dibasic alcohol of small-molecular-weight is vacuumized except water under 60 DEG C��80 DEG C conditions, and then under protection of inert gas, carry out chain extending reaction with isocyanic ester; obtain carbonic acid gas based polyurethanes; carrying out smoothly to react, the present invention is it is also preferred that add catalyzer, and described catalyzer is preferably dibutyltin dilaurate catalyst.
In order to obtain the higher carbonic acid gas based polyurethanes of purity, the carbonic acid gas based polyurethanes being obtained by reacting and acetone are preferably preferably 1:1.5��2.5 and mix by the present invention by volume, low whipping speed stirs the mixing solutions of described carbonic acid gas based polyurethanes and acetone under being preferably 100��150rpm, then slowly dripping with acetone volume ratio is the aqueous solution of 1:3.5��5.5, leave standstill 0.5��1h, topple over supernatant liquor, obtain the carbonic acid gas based polyurethanes of purifying, the carbonic acid gas based polyurethanes of purifying is dried under 30��50 DEG C of conditions, obtain dry carbonic acid gas based polyurethanes, the device dried is not particularly limited by the present invention, the convection oven that art technology field personnel know, electric oven, infrared heating oven.
The blend of carbon dioxide-epoxy propane copolymer provided by the invention, carbon dioxide-base polyurethanes compound and carbon dioxide-epoxy propane copolymer is used to carry out blended, owing to carbonic acid gas based polyurethanes is obtained by the carbon dioxide-epoxy propane copolymer polyvalent alcohol of lower molecular weight and isocyanic ester chain extending reaction, make carbonic acid gas based polyurethanes can have good consistency with carbon dioxide-epoxy propane copolymer, and then improve the interfacial adhesion of blend, stress is effectively transmitted in interface, so that the blend of carbon dioxide-epoxy propane copolymer provided by the invention not only tensile strength and Young's modulus height, and elongation at break is also higher.
Present invention also offers the preparation method of the blend of a kind of carbon dioxide-epoxy propane copolymer, comprising:
A) the carbonic acid gas based polyurethanes of 2.5��20 weight parts is mixed with the carbon dioxide-epoxy propane copolymer of 80��97.5 weight parts, obtain mixture;
The structure of described carbonic acid gas based polyurethanes such as formula shown in I,
Wherein, x is 10%��90%, y is 90%��10%, and x+y=1;
Z is 2��30;
N is 35��100;
R is the structure shown in formula (II), formula (III) or formula (IV),
Wherein, * is link position, and i is the integer of 2��8;
R1For the structure shown in formula (V), formula (VI), formula (VII), formula (VIII), formula (IX), formula (X), formula (XI) or formula (XII),
Wherein, * is link position, and j is the integer of 1��10;
B) by mixture melt blending, the blend of carbon dioxide-epoxy propane copolymer is obtained.
According to the present invention, the carbonic acid gas based polyurethanes of 2.5��20 weight parts is mixed by the present invention with the carbon dioxide-epoxy propane copolymer of 80��97.5 weight parts, obtains mixture; In order to make mixing more abundant, the present invention is preferably by described solid mixture freeze-day with constant temperature 24h at 38��42 DEG C, then dried mixture is carried out further married operation, the rotating speed of mixing of the present invention is preferably 800��1500rpm, mixing time is preferably 5��8h, and the mixing of this step is the abundant mixing to polymkeric substance and completes preliminary plasticizing. The equipment of mixing is not had particular requirement by the present invention, it is preferable to kneader well known in the art, high-speed mixer, static mixer or ribbon mixer, it is more preferable to be high-speed mixer.
In this preparation method, the number-average molecular weight of described carbonic acid gas based polyurethanes is preferably 30000��80000, it is more preferable to be 40000��60000; The molecular weight distributing index of described carbonic acid gas based polyurethanes is preferably 1.5��3.0, it is more preferable to be 1.6��2.0; The number-average molecular weight of described carbon dioxide-epoxy propane copolymer is preferably 50000��300000, it is more preferable to be 1000000��200000; The molecular weight distributing index of described carbon dioxide-epoxy propane copolymer is preferably 1.2��4.5; Described carbonic acid gas based polyurethanes content in the blend is preferably 3��18 weight parts, it is more preferable to be 5��15 weight parts; Described carbon dioxide-epoxy propane copolymer content in the blend is preferably 82��97 weight parts, it is more preferable to be 85��95 weight parts.
In preparation method provided by the invention, in the structure of the formula (I) shown in described carbonic acid gas based polyurethanes, described i is preferably 4��7, it is more preferable to be 4,5 or 6; Described j is preferably 2��8, it is more preferable to be 3,4,5,6,7; The source of described carbonic acid gas based polyurethanes is not had particular requirement by the present invention, it is preferable that prepare in accordance with the following methods:
By the carbon dioxide-epoxy propane copolymer dibasic alcohol of small-molecular-weight and isocyanic ester hybrid reaction, obtain carbonic acid gas based polyurethanes.
Concrete, the carbon dioxide-epoxy propane copolymer dibasic alcohol of small-molecular-weight and isocyanic ester hybrid reaction, the molecular weight of the carbon dioxide-epoxy propane copolymer dibasic alcohol of described small-molecular-weight is 1000��2000 by the present invention, and molecular weight distribution is 1.0��1.5; Carbonate content in the carbon dioxide-epoxy propane copolymer dibasic alcohol of described small-molecular-weight is preferably 30%, 40%, 50% or 60%; Described isocyanic ester be preferably in tolylene diisocyanate, hexamethylene diisocyanate and diphenylmethanediisocyanate one or more, it is more preferable to be tolylene diisocyanate; The carbon dioxide-epoxy propane copolymer dibasic alcohol of described small-molecular-weight and the mass ratio of described isocyanic ester are (1.5��0.7): (1.3��0.8), the temperature of described hybrid reaction is preferably 100��110 DEG C, and the time of described hybrid reaction is preferably 0.25��1 hour.
Further; better carry out to react; the present invention is preferably before hybrid reaction; first the carbon dioxide-epoxy propane copolymer dibasic alcohol of small-molecular-weight is vacuumized except water under 60 DEG C��80 DEG C conditions, and then under protection of inert gas, carry out chain extending reaction with isocyanic ester; obtain carbonic acid gas based polyurethanes; carrying out smoothly to react, the present invention is it is also preferred that add catalyzer, and described catalyzer is preferably dibutyltin dilaurate catalyst.
In order to obtain the higher carbonic acid gas based polyurethanes of purity, the carbonic acid gas based polyurethanes being obtained by reacting and acetone are preferably preferably 1:1.5��2.5 and mix by the present invention by volume, low whipping speed stirs the mixing solutions of described carbonic acid gas based polyurethanes and acetone under being preferably 100��150rpm, then slowly dripping with acetone volume ratio is the aqueous solution of 1:3.5��5.5, leave standstill 0.5��1h, topple over supernatant liquor, obtain the carbonic acid gas based polyurethanes of purifying, the carbonic acid gas based polyurethanes of purifying is dried under 30��50 DEG C of conditions, obtain dry carbonic acid gas based polyurethanes, the device dried is not particularly limited by the present invention, the convection oven that art technology field personnel know, electric oven, infrared heating oven.
According to the present invention, by mixture melt blending, obtaining the blend of carbon dioxide-epoxy propane copolymer, the temperature of described melt blending is preferably 120��230 DEG C, it is more preferable to be 140��200 DEG C; The time of described melt blending is preferably 2��7min, it is more preferable in 3��5min, and the rotating speed of described melt blending is preferably 30��80rpm, it is more preferable to be 50��70rpm.
Present invention also offers the preparation method of the blend of a kind of carbon dioxide-epoxy propane copolymer, it may also be useful to small-molecular-weight dibasic alcohol and isocyanic ester chain extension synthesis of polyurethane, technique is simple, with low cost, is applicable to suitability for industrialized production; Meanwhile, described carbon dioxide-epoxy propane copolymer and carbonic acid gas based polyurethanes are undertaken blended by the method for melting after mixing, and condition is easy to control.
Below in conjunction with the embodiment of the present invention, the technical scheme of the present invention is clearly and completely described, it is clear that described embodiment is only the present invention's part embodiment, instead of whole embodiments. Based on the embodiment in the present invention, those of ordinary skill in the art, not making other embodiments all obtained under creative work prerequisite, belong to the scope of protection of the invention.
Raw material sources: the method preparation that the PPC that the present invention uses introduces according to Chinese patent CN1094945, CN100381480, CN1116332, are provided by Meng Xi new and high technology group company and Taizhou, Zhejiang Bang Feng plastics company limited.
Embodiment 1
Adding number-average molecular weight in 250ml round-bottomed flask is 1500, carbonate content is carbon dioxide-epoxy propane copolymer dibasic alcohol 45g (0.03mol) of 50%, vaccum dewatering 30min at temperature is 80 DEG C, then under nitrogen (nitrogen gas purity is 99.99%) is protected, 4.3ml (0.035mol) tolylene diisocyanate and 3 �� L dibutyltin dilaurate catalysts are added in described round-bottomed flask, round-bottomed flask is placed in thermostatic control bath, control temperature is 100 DEG C, the reactant 20min in round-bottomed flask is stirred with the speed of 90rpm, flask is placed in frozen water cooling. in flask, add the acetone of 50ml, stir with the speed of 120rpm and polymkeric substance is fully dissolved, under 60rpm stirs, in system, slowly add 200ml deionized water. incline supernatant liquor, and polymkeric substance sedimentation gone out to constant weight, obtains carbonic acid gas based polyurethanes 1 40 DEG C of vacuum oven.
Carrying out molecular weight determination by the carbonic acid gas based polyurethanes 1 embodiment 1 prepared, result shows, its number-average molecular weight is 43000, and molecular weight distribution is 1.68.
Infrared analysis is carried out, the infrared spectrogram of the carbonic acid gas based polyurethanes that result provides for the embodiment of the present invention 1 see Fig. 1, Fig. 1 by the carbonic acid gas based polyurethanes 1 embodiment 1 prepared.
Embodiment 2
Adding number-average molecular weight in 250ml round-bottomed flask is 1330, carbonate content is carbon dioxide-epoxy propane copolymer dibasic alcohol 40g (0.03mol) of 60%, vaccum dewatering 30min at temperature is 80 DEG C, then under nitrogen (nitrogen gas purity is 99.99%) is protected, 4.3ml (0.035mol) tolylene diisocyanate and 3 �� L dibutyltin dilaurate catalysts are added in described round-bottomed flask, round-bottomed flask is placed in thermostatic control bath, control temperature is 1000C, the reactant 20min in round-bottomed flask is stirred with the speed of 90rpm, flask is placed in frozen water cooling. in flask, add the acetone of 50ml, stir with the speed of 120rpm and polymkeric substance is fully dissolved, under 60rpm stirs, in system, slowly add 200ml deionized water. incline supernatant liquor, and polymkeric substance sedimentation gone out to constant weight, obtains carbonic acid gas based polyurethanes 2 40 DEG C of vacuum oven.
Carrying out molecular weight determination by the carbonic acid gas based polyurethanes 2 embodiment 2 prepared, result shows, its number-average molecular weight is 54000, and molecular weight distribution is 1.84.
Infrared analysis is carried out, the infrared spectrogram of the carbonic acid gas based polyurethanes that result provides for the embodiment of the present invention 2 see Fig. 2, Fig. 2 by the carbonic acid gas based polyurethanes 2 embodiment 2 prepared.
Embodiment 3
Take 48.75g carbon dioxide-epoxy propane copolymer (its Mn=186000 respectively, PDI=3.26, elongation at break is 9.83%, tensile strength is 53.47Mpa, non-notched Izod impact strength is 8.14KJ/m2) and 1.25g embodiment 1 prepare carbonic acid gas based polyurethanes 1, through simple mixing, obtain solid mixture. After vacuum-drying 24h, described solid mixture is placed in high-speed mixer mixing 5min in 40 DEG C of vacuum drying ovens, and high-speed mixer rotating speed is 1000rpm; Solid mixture after mixing is placed in HAAKE torque rheometer and carries out banburying, and the banburying time is 5min, and Banbury mixer rotating speed is 60rpm, and temperature is 140 DEG C. Obtain the blend 3 of carbon dioxide-epoxy propane copolymer.
Blend embodiment prepared is at 140 DEG C of condition lower sheeting 3min, and cold pressing 1min, obtains the blend section bar of carbon dioxide-epoxy propane copolymer;
Section bar embodiment prepared tests its mechanical property by GB-T1040-92, result is see table 1, the performance test results of the blend section bar of the carbon dioxide-epoxy propane copolymer that table 1 provides for the embodiment of the present invention, result shows, the tensile strength of blend prepared by embodiment 3 is 59.83MPa, elongation at break is 24.60%, and non-notched Izod impact strength is 9.34KJ/m2.
Embodiment 4
Take 47.5g carbon dioxide-epoxy propane copolymer (its Mn=186000 respectively, PDI=3.26, elongation at break is 9.83%, tensile strength is 53.47Mpa, non-notched Izod impact strength is 8.14KJ/m2) and 2.5g embodiment 1 prepare carbonic acid gas based polyurethanes 1, through simple mixing, obtain solid mixture. After vacuum-drying 24h, described solid mixture is placed in high-speed mixer mixing 5min in 400C vacuum drying oven, and high-speed mixer rotating speed is 1000rpm. Solid mixture after mixing is placed in HAAKE torque rheometer and carries out banburying, and the banburying time is 5min, and Banbury mixer rotating speed is 60rpm, and temperature is 1400C, obtains the blend 4 of carbon dioxide-epoxy propane copolymer.
Blend embodiment prepared is at 140 DEG C of condition lower sheeting 3min, and cold pressing 1min, obtains the blend section bar of carbon dioxide-epoxy propane copolymer;
Section bar embodiment prepared tests its mechanical property by GB-T1040-92, result is see table 1, the performance test results of the blend section bar of the carbon dioxide-epoxy propane copolymer that table 1 provides for the embodiment of the present invention, result shows, the tensile strength of blend prepared by embodiment 4 is 63.68MPa, elongation at break is 28.74%, and non-notched Izod impact strength is 10.09KJ/m2.
Embodiment 5
Take 45g carbon dioxide-epoxy propane copolymer (its Mn=186000 respectively, PDI=3.26, elongation at break is 9.83%, tensile strength is 53.47Mpa, non-notched Izod impact strength is 8.14KJ/m2) and 5g embodiment 1 prepare carbonic acid gas based polyurethanes 1, through simple mixing, obtain solid mixture. After vacuum-drying 24h, described solid mixture is placed in high-speed mixer mixing 5min in 400C vacuum drying oven, and high-speed mixer rotating speed is 1000rpm. Solid mixture after mixing is placed in HAAKE torque rheometer and carries out banburying, and the banburying time is 5min, and Banbury mixer rotating speed is 60rpm, and temperature is 1400C, obtains the blend 5 of carbon dioxide-epoxy propane copolymer.
Blend embodiment prepared is at 140 DEG C of condition lower sheeting 3min, and cold pressing 1min, obtains the blend section bar of carbon dioxide-epoxy propane copolymer;
Section bar embodiment prepared tests its mechanical property by GB-T1040-92, result is see table 1, the performance test results of the blend section bar of the carbon dioxide-epoxy propane copolymer that table 1 provides for the embodiment of the present invention, result shows, the tensile strength of blend prepared by embodiment 5 is 60.69MPa, elongation at break is 28.71%, and non-notched Izod impact strength is 9.89KJ/m2.
Embodiment 6
Take 42.5g carbon dioxide-epoxy propane copolymer (its Mn=186000 respectively, PDI=3.26, elongation at break is 9.83%, tensile strength is 53.47Mpa, non-notched Izod impact strength is 8.14KJ/m2) and 7.5g embodiment 1 prepare carbonic acid gas based polyurethanes 1, through simple mixing, obtain solid mixture. After vacuum-drying 24h, described solid mixture is placed in high-speed mixer mixing 5min in 400C vacuum drying oven, and high-speed mixer rotating speed is 1000rpm. Solid mixture after mixing is placed in HAAKE torque rheometer and carries out banburying, and the banburying time is 5min, and Banbury mixer rotating speed is 60rpm, and temperature is 1400C, obtains the blend 6 of carbon dioxide-epoxy propane copolymer.
Blend embodiment prepared is at 140 DEG C of condition lower sheeting 3min, and cold pressing 1min, obtains the blend section bar of carbon dioxide-epoxy propane copolymer;
Section bar embodiment prepared tests its mechanical property by GB-T1040-92, result is see table 1, the performance test results of the blend section bar of the carbon dioxide-epoxy propane copolymer that table 1 provides for the embodiment of the present invention, result shows, the tensile strength of blend prepared by embodiment 6 is 50.92MPa, elongation at break is 27.26%, and non-notched Izod impact strength is 11.46KJ/m2.
Embodiment 7
Take 40g carbon dioxide-epoxy propane copolymer (its Mn=186000 respectively, PDI=3.26, elongation at break is 9.83%, tensile strength is 53.47Mpa, non-notched Izod impact strength is 8.14KJ/m2) and 10g embodiment 1 prepare carbonic acid gas based polyurethanes 1, through simple mixing, obtain solid mixture. After vacuum-drying 24h, described solid mixture is placed in high-speed mixer mixing 5min in 400C vacuum drying oven, and high-speed mixer rotating speed is 1000rpm. Solid mixture after mixing is placed in HAAKE torque rheometer and carries out banburying, and the banburying time is 5min, and Banbury mixer rotating speed is 60rpm, and temperature is 1400C, obtains the blend 7 of carbon dioxide-epoxy propane copolymer.
Blend embodiment prepared is at 140 DEG C of condition lower sheeting 3min, and cold pressing 1min, obtains the blend section bar of carbon dioxide-epoxy propane copolymer;
Section bar embodiment prepared tests its mechanical property by GB-T1040-92, result is see table 1, the performance test results of the blend section bar of the carbon dioxide-epoxy propane copolymer that table 1 provides for the embodiment of the present invention, result shows, the tensile strength of blend prepared by embodiment 7 is 47.66MPa, elongation at break is 49.48%, and non-notched Izod impact strength is 66.39KJ/m2.
Embodiment 8
Take 48.75g carbon dioxide-epoxy propane copolymer (its Mn=186000 respectively, PDI=3.26, elongation at break is 9.83%, tensile strength is 53.47Mpa, non-notched Izod impact strength is 8.14KJ/m2) and 1.25g embodiment 2 prepare carbonic acid gas based polyurethanes 2, through simple mixing, obtain solid mixture. After vacuum-drying 24h, described solid mixture is placed in high-speed mixer mixing 5min in 400C vacuum drying oven, and high-speed mixer rotating speed is 1000rpm. Solid mixture after mixing is placed in HAAKE torque rheometer and carries out banburying, and the banburying time is 5min, and Banbury mixer rotating speed is 60rpm, and temperature is 1400C, obtains the blend 8 of carbon dioxide-epoxy propane copolymer.
Blend embodiment prepared is at 140 DEG C of condition lower sheeting 3min, and cold pressing 1min, obtains the blend section bar of carbon dioxide-epoxy propane copolymer;
Section bar embodiment prepared tests its mechanical property by GB-T1040-92, result is see table 1, the performance test results of the blend section bar of the carbon dioxide-epoxy propane copolymer that table 1 provides for the embodiment of the present invention, result shows, the tensile strength of blend prepared by embodiment 8 is 61.99MPa, elongation at break is 21.97%, and non-notched Izod impact strength is 8.14KJ/m2.
Embodiment 9
Take 47.5g carbon dioxide-epoxy propane copolymer (its Mn=186000 respectively, PDI=3.26, elongation at break is 9.83%, tensile strength is 53.47Mpa, non-notched Izod impact strength is 8.14KJ/m2) and 2.5g embodiment 2 prepare carbonic acid gas based polyurethanes 2, through simple mixing, obtain solid mixture. After vacuum-drying 24h, described solid mixture is placed in high-speed mixer mixing 5min in 400C vacuum drying oven, and high-speed mixer rotating speed is 1000rpm. Solid mixture after mixing is placed in HAAKE torque rheometer and carries out banburying, and the banburying time is 5min, and Banbury mixer rotating speed is 60rpm, and temperature is 1400C, obtains the blend 9 of carbon dioxide-epoxy propane copolymer.
Blend embodiment prepared is at 140 DEG C of condition lower sheeting 3min, and cold pressing 1min, obtains the blend section bar of carbon dioxide-epoxy propane copolymer;
Section bar embodiment prepared tests its mechanical property by GB-T1040-92, result is see table 1, the performance test results of the blend section bar of the carbon dioxide-epoxy propane copolymer that table 1 provides for the embodiment of the present invention, result shows, the tensile strength of blend prepared by embodiment 9 is 63.28MPa, elongation at break is 22.37%, and non-notched Izod impact strength is 9.85KJ/m2.
Embodiment 10
Take 45g carbon dioxide-epoxy propane copolymer (its Mn=186000 respectively, PDI=3.26, elongation at break is 9.83%, tensile strength is 53.47Mpa, non-notched Izod impact strength is 8.14KJ/m2) and 5g embodiment 2 prepare carbonic acid gas based polyurethanes 2, through simple mixing, obtain solid mixture. After vacuum-drying 24h, described solid mixture is placed in high-speed mixer mixing 5min in 400C vacuum drying oven, and high-speed mixer rotating speed is 1000rpm. Solid mixture after mixing is placed in HAAKE torque rheometer and carries out banburying, and the banburying time is 5min, and Banbury mixer rotating speed is 60rpm, and temperature is 1400C, obtains the blend 10 of carbon dioxide-epoxy propane copolymer.
Blend embodiment prepared is at 140 DEG C of condition lower sheeting 3min, and cold pressing 1min, obtains the blend section bar of carbon dioxide-epoxy propane copolymer;
Section bar embodiment prepared tests its mechanical property by GB-T1040-92, result is see table 1, the performance test results of the blend section bar of the carbon dioxide-epoxy propane copolymer that table 1 provides for the embodiment of the present invention, result shows, the tensile strength of blend prepared by embodiment 10 is 66.23MPa, elongation at break is 20.22%, and non-notched Izod impact strength is 10.90KJ/m2.
Embodiment 11
Take 42.5g carbon dioxide-epoxy propane copolymer (its Mn=186000 respectively, PDI=3.26, elongation at break is 9.83%, tensile strength is 53.47Mpa, non-notched Izod impact strength is 8.14KJ/m2) and 7.5g embodiment 2 prepare carbonic acid gas based polyurethanes 2, through simple mixing, obtain solid mixture. After vacuum-drying 24h, described solid mixture is placed in high-speed mixer mixing 5min in 400C vacuum drying oven, and high-speed mixer rotating speed is 1000rpm. Solid mixture after mixing is placed in HAAKE torque rheometer and carries out banburying, and the banburying time is 5min, and Banbury mixer rotating speed is 60rpm, and temperature is 1400C, obtains the blend 11 of carbon dioxide-epoxy propane copolymer.
Blend embodiment prepared is at 140 DEG C of condition lower sheeting 3min, and cold pressing 1min, obtains the blend section bar of carbon dioxide-epoxy propane copolymer;
Section bar embodiment prepared tests its mechanical property by GB-T1040-92, result is see table 1, the performance test results of the blend section bar of the carbon dioxide-epoxy propane copolymer that table 1 provides for the embodiment of the present invention, result shows, the tensile strength of blend prepared by embodiment 11 is 63.78MPa, elongation at break is 33.74%, and non-notched Izod impact strength is 10.83KJ/m2.
Embodiment 12
Take 40g carbon dioxide-epoxy propane copolymer (its Mn=186000 respectively, PDI=3.26, elongation at break is 9.83%, tensile strength is 53.47Mpa, non-notched Izod impact strength is 8.14KJ/m2) and 10g embodiment 2 prepare carbonic acid gas based polyurethanes 2, through simple mixing, obtain solid mixture. After vacuum-drying 24h, described solid mixture is placed in high-speed mixer mixing 5min in 400C vacuum drying oven, and high-speed mixer rotating speed is 1000rpm. Solid mixture after mixing is placed in HAAKE torque rheometer and carries out banburying, and the banburying time is 5min, and Banbury mixer rotating speed is 60rpm, and temperature is 1400C, obtains the blend 12 of carbon dioxide-epoxy propane copolymer.
Blend embodiment prepared is at 140 DEG C of condition lower sheeting 3min, and cold pressing 1min, obtains the blend section bar of carbon dioxide-epoxy propane copolymer;
Section bar embodiment prepared tests its mechanical property by GB-T1040-92, result is see table 1, the performance test results of the blend section bar of the carbon dioxide-epoxy propane copolymer that table 1 provides for the embodiment of the present invention, result shows, the tensile strength of blend prepared by embodiment 12 is 57.79MPa, elongation at break is 33.06%, and non-notched Izod impact strength is 10.70KJ/m2.
The performance test results of the blend section bar of the carbon dioxide-epoxy propane copolymer that table 1 provides for the embodiment of the present invention
The toughness of elongation at break exosyndrome material, the rigidity of tensile strength exosyndrome material, as can be seen from Table 1, by blended to carbonic acid gas based polyurethanes and the carbon dioxide-epoxy propane copolymer blend obtained, elongation at break has lifting in various degree, and tensile strength decline simultaneously is little, is even significantly increased, therefore, add carbonic acid gas based polyurethanes of the present invention and can realize the toughen and intensify to carbon dioxide-epoxy propane copolymer simultaneously.
Illustrating just for helping the method understanding the present invention and core concept thereof of above embodiment. , it is also possible to the present invention carries out some improvement and modification, it is noted that for those skilled in the art, under the premise without departing from the principles of the invention these improve and modify in the protection domain also falling into the claims in the present invention.
Claims (10)
1. a blend for carbon dioxide-epoxy propane copolymer, in weight fraction, comprising:
The carbonic acid gas based polyurethanes of 2.5��20 weight parts;
The carbon dioxide-epoxy propane copolymer of 80��97.5 weight parts;
The structure of described carbonic acid gas based polyurethanes such as formula shown in I,
Wherein, x is 10%��90%, y is 90%��10%, and x+y=1;
Z is 2��30;
N is 35��100;
R is the structure shown in formula (II), formula (III) or formula (IV),
Wherein, * is link position, and i is the integer of 2��8;
R1For the structure shown in formula (V), formula (VI), formula (VII), formula (VIII), formula (IX), formula (X), formula (XI) or formula (XII),
Wherein, * is link position, and j is the integer of 1��10.
2. blend according to claim 1, it is characterised in that, the number-average molecular weight of described carbonic acid gas based polyurethanes is 30000��80000, and molecular weight distributing index is 1.5��3.0.
3. blend according to claim 1, it is characterised in that, the number-average molecular weight of described carbon dioxide-epoxy propane copolymer is 50000��300000, and molecular weight distributing index is 1.2��4.5.
4. a preparation method for the blend of carbon dioxide-epoxy propane copolymer, comprising:
A) the carbonic acid gas based polyurethanes of 2.5��20 weight parts is mixed with the carbon dioxide-epoxy propane copolymer of 80��97.5 weight parts, obtain mixture;
The structure of described carbonic acid gas based polyurethanes such as formula shown in I,
Wherein, x is 10%��90%, y is 90%��10%, and x+y=1;
Z is 2��30;
N is 35��100;
R is the structure shown in formula (II), formula (III) or formula (IV),
Wherein, * is link position, and i is the integer of 2��8;
R1For the structure shown in formula (V), formula (VI), formula (VII), formula (VIII), formula (IX), formula (X), formula (XI) or formula (XII),
Wherein, * is link position, and j is the integer of 1��10;
B) by mixture melt blending, the blend of carbon dioxide-epoxy propane copolymer is obtained.
5. preparation method according to claim 4, it is characterised in that, the number-average molecular weight of described carbonic acid gas based polyurethanes is 30000��80000, and molecular weight distributing index is 1.5��3.0.
6. preparation method according to claim 4, it is characterised in that, the number-average molecular weight of described carbon dioxide-epoxy propane copolymer is 50000��300000, and molecular weight distributing index is 1.2��4.5.
7. preparation method according to claim 4, it is characterised in that, the temperature of described melt blending is 120 DEG C��230 DEG C.
8. preparation method according to claim 4, it is characterised in that, described carbonic acid gas based polyurethanes is prepared in accordance with the following methods:
By the carbon dioxide-epoxy propane copolymer dibasic alcohol of small-molecular-weight and isocyanic ester hybrid reaction, obtain carbonic acid gas based polyurethanes.
9. preparation method according to claim 8, it is characterised in that, the molecular weight of the carbon dioxide-epoxy propane copolymer dibasic alcohol of described small-molecular-weight is 1000��2000, and molecular weight distribution is 1.0��1.5.
10. preparation method according to claim 8, it is characterised in that, the carbon dioxide-epoxy propane copolymer dibasic alcohol of described small-molecular-weight and the mass ratio of described isocyanic ester are (1.5��0.7): (1.3��0.8).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410449423.1A CN104177805B (en) | 2014-09-04 | 2014-09-04 | The blend of carbon dioxide-epoxy propane copolymer and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410449423.1A CN104177805B (en) | 2014-09-04 | 2014-09-04 | The blend of carbon dioxide-epoxy propane copolymer and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104177805A CN104177805A (en) | 2014-12-03 |
| CN104177805B true CN104177805B (en) | 2016-06-01 |
Family
ID=51959167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410449423.1A Active CN104177805B (en) | 2014-09-04 | 2014-09-04 | The blend of carbon dioxide-epoxy propane copolymer and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104177805B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105482385B (en) * | 2016-01-20 | 2018-06-29 | 中国科学院长春应用化学研究所 | A kind of biodegradation agricultural mulching and preparation method thereof |
| CN106674970B (en) * | 2017-01-05 | 2019-08-16 | 广东工业大学 | A kind of poly (propylene carbonate)/PPC type polyurethane elastomer high strength composite and preparation method thereof |
| CN106674994B (en) * | 2017-01-05 | 2019-11-08 | 广东工业大学 | A kind of poly (propylene carbonate)/polyester polyurethane elastic composite and preparation method thereof |
| CN109485818B (en) * | 2018-11-13 | 2021-06-25 | 南京林业大学 | Self-repairable polyurethane elastomer and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1400229A (en) * | 2002-08-30 | 2003-03-05 | 中国科学院广州化学研究所 | Polyurethane foam material and its preparation method |
| CN103289349A (en) * | 2013-06-28 | 2013-09-11 | 南通华盛高聚物科技发展有限公司 | Biodegradable resin composition |
-
2014
- 2014-09-04 CN CN201410449423.1A patent/CN104177805B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1400229A (en) * | 2002-08-30 | 2003-03-05 | 中国科学院广州化学研究所 | Polyurethane foam material and its preparation method |
| CN103289349A (en) * | 2013-06-28 | 2013-09-11 | 南通华盛高聚物科技发展有限公司 | Biodegradable resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104177805A (en) | 2014-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104177805B (en) | The blend of carbon dioxide-epoxy propane copolymer and its preparation method | |
| CN100378138C (en) | Process for improving friability and cold-flow of carbon dioxide epoxy propylane copolymer | |
| CN102702705A (en) | Toughened polylactic acid/polyolefin elastomer composite material and preparation method thereof | |
| CN1737028A (en) | Cellulosine plastic composite compatiblizing agent and method for making same | |
| CN102690444B (en) | Starch-base biodegradable resin composition and preparation method thereof | |
| CN108822245A (en) | （Methyl）Acrylic copolymer | |
| CN108192316A (en) | High fluidity high tenacity polycarbonate/polyethylene terephthalate alloy and preparation method thereof | |
| CN102731921A (en) | Weatherproof polymer alloy used for replacing ABS | |
| CN110938291A (en) | Polylactic acid composite material and preparation method thereof | |
| CN110922730B (en) | Modified polylactic acid and preparation method thereof | |
| CN102153849B (en) | Aliphatic polycarbonate alloy material | |
| CN117164977A (en) | PE composite plastic and preparation method thereof | |
| CN103951960B (en) | A kind of modification polypropylene carbonate and preparation method thereof | |
| CN110054838A (en) | A kind of cellulose hydridization filler enhancing polymer composites and preparation method thereof | |
| CN103897356B (en) | The resistant to elevated temperatures thermoplastic polyester elastomer composition of a kind of hydrolysis | |
| CN103910936A (en) | PP/EPDM (polypropylene/ethylene-propylene-diene monomer) composite material and preparation method thereof | |
| AU601609B2 (en) | Poly(alkylene terephthalate) compositions having improved crystallization rate and properties | |
| CN102994033B (en) | Polyester adhesive | |
| CN102070893A (en) | Blend of carbon dioxide-propylene oxide copolymers and preparation method thereof | |
| CN113136104B (en) | Polyphenylene sulfide/nylon 6 composite material and preparation method thereof | |
| CN101665610B (en) | Alloy material composition and alloy material | |
| CN101240108B (en) | Polylactic acid-organic soapstone composite material and preparation method thereof | |
| CN103408906B (en) | A kind of high plant degree high-performance polylactic acid alloy material | |
| CN117511152B (en) | Environment-friendly polylactic acid plastic and preparation method and application thereof | |
| CN115960417B (en) | Plant fiber reinforced polypropylene material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |