TWI718592B - Preparing method of polyamide-imide - Google Patents

Abstract

A polyamide-imide is provided. The polyamide-imide is represented by formula 1:

wherein R is a C₆ aryl group, a C₇-C₈ aralkyl group, a C₂-C₃ alkoxyalkyl group, or a C₃-C₁₈ alkyl group; and 0.02

X

Description

Preparation method of polyamide imine

The present invention relates to a polymer, and particularly relates to a polyamide imide and a preparation method thereof.

Due to its excellent heat resistance, chemical resistance, flame resistance and other properties, many thermoplastic resins called "engineering plastics" have been widely used in various fields. However, engineering plastics still have limitations in their use. For example, the processing temperature of polyetherimide is quite high (between 350 and 380°C), which is not easy to achieve for general machines. In addition, when polyvinylidene fluoride is subjected to high-temperature molding, if the processing temperature reaches 320°C or higher, hydrofluoric acid, which is highly corrosive, is likely to be generated. Therefore, how to improve the applicability of engineering plastics is still an important subject of active research.

The present invention provides a polyamide imide and a preparation method thereof. The polyamide imide has good thermal processing properties and a reduced thermal processing temperature.

The polyimide imine of the present invention is represented by the following formula 1:

X

0.5。 Formula 1, wherein R is an aryl group having a carbon number of 6, an aralkyl group having a carbon number of 7 to 8, an alkoxyalkyl group having a carbon number of 2 to 6, or an alkyl group having a carbon number of 3 to 18; and 0.02

X

0.5.

In an embodiment of the present invention, the above-mentioned R is selected from one of the groups represented by formula a to formula g:

，其中在式a至式g中，*表示鍵結位置。

, Where in formula a to formula g, * represents the bonding position.

In an embodiment of the present invention, the weight average molecular weight of the above-mentioned polyamide imine is between 47000 g/mol and 55000 g/mol.

The preparation method of polyimide imine of the present invention includes the following steps. The polyimide dissolved in the solvent is reacted with the modifier to form a first solution containing the polyimide, wherein the polyimide includes a repeating unit represented by the following formula I, and the modifier is composed of Formula II represents that polyamide imine is represented by the following formula 1:

NH ₂ R formula II

X

0.5。將非溶劑加入含有聚醯胺醯亞胺的第一溶液中，以使聚醯胺醯亞胺自第一溶液析出。 Formula 1, wherein the weight average molecular weight of polyimine is between 44000g/mol and 50000g/mol; R is an aryl group with a carbon number of 6, an aralkyl group with a carbon number of 7 to 8, and a carbon number of from 2 to An alkoxyalkyl group of 6 or an alkyl group having 3 to 18 carbon atoms; and 0.02

X

0.5. A non-solvent is added to the first solution containing the polyimide, so that the polyimide is precipitated from the first solution.

In an embodiment of the present invention, the above-mentioned R is selected from one of the groups represented by formula a to formula g:

，其中在式a至式g中，*表示鍵結位置。

, Where in formula a to formula g, * represents the bonding position.

In an embodiment of the present invention, the weight average molecular weight of the above-mentioned polyamide imine is between 47000 g/mol and 55000 g/mol.

In an embodiment of the present invention, the aforementioned solvent includes N,N-dimethylacetamide (DMAc), N-methylpyrrolidone or tetrahydrofuran.

In an embodiment of the present invention, the aforementioned non-solvent includes methanol, ethanol, isopropanol or water.

In one embodiment of the present invention, the above-mentioned preparation method of polyimide further comprises: before adding the non-solvent to the first solution containing polyimide imine, using a diluent to The first solution of imine is diluted to form a second solution containing polyimide.

In one embodiment of the present invention, the viscosity of the first solution containing polyimide is between 1000 cps and 10000 cps, and the viscosity of the second solution containing polyimide is between 10 cps and Between 200cps.

In an embodiment of the present invention, the ratio of the weight average molecular weight of the above-mentioned polyimide to the weight average molecular weight of the above-mentioned polyimide is between 2.2 and 2.6.

In an embodiment of the present invention, the reaction temperature of the reaction between the polyimide and the modifier is between 30°C and 100°C.

Based on the above, the preparation method of polyimide of the present invention involves the following steps: reacting the modifier represented by the above formula II with the polyimide represented by the above formula I to form a polyimide containing polyimide A solution of imine, and adding a non-solvent to the solution, whereby the polyimide represented by Formula 1 above can be prepared. In addition, based on the structure shown in Formula 1, it can be seen that the polyamideimide of the present invention has a ring-opening structure and the free volume of the molecule increases, whereby the polyamideimide can have good thermal processability and reduced Thermal processing temperature.

In order to make the above-mentioned features and advantages of the present invention more comprehensible, the following specific embodiments are described in detail in conjunction with the accompanying drawings.

S10, S12, S20: steps

Fig. 1 is a schematic flow chart of a preparation method of polyamideimines according to an embodiment of the present invention.

Fig. 2 is a schematic flow chart of a preparation method of polyamideimines according to another embodiment of the present invention.

In this article, the range represented by "a value to another value" is a general way to avoid listing all the values in the range one by one in the specification. formula. Therefore, the record of a specific numerical range covers any numerical value in the numerical range and the smaller numerical range defined by any numerical value in the numerical range, as if the arbitrary numerical value and the smaller numerical value are clearly written in the specification The scope is the same.

In this text, the skeleton formula is sometimes used to represent the structure of a polymer or group. This notation can omit carbon atoms, hydrogen atoms, and carbon-hydrogen bonds. Of course, if atoms or atomic groups are clearly drawn in the structural formula, the drawn ones shall prevail.

As used herein, "approximately", "approximately", "essentially", or "substantially" includes the stated value and the average value within the acceptable deviation range of the specific value determined by a person of ordinary skill in the art, taking into account all The measurement in question and the specific number of errors associated with the measurement (ie, the limitations of the measurement system). For example, "about" can mean within one or more standard deviations of the stated value, or, for example, within ±30%, ±20%, ±15%, ±10%, ±5%. Furthermore, the "approximate", "approximate", "essential", or "substantially" used in this article can be used to select a more acceptable range of deviation or standard deviation based on the nature of the measurement or other properties, instead of using a standard The deviation applies to all properties.

In order to provide a polyamide imide with good thermal processability and a reduced thermal processing temperature, the present invention proposes a preparation method of polyamide imide, the prepared polyamide imide can achieve the above advantage. Hereinafter, the specific embodiments are cited as examples on which the present invention can be implemented.

Fig. 1 is a schematic flow chart of a preparation method of polyamideimines according to an embodiment of the present invention. 1, first, step S10 is performed to react the modifier with the polyimide dissolved in the solvent to form a polyimide-containing solvent liquid. That is, in this embodiment, the polyimide is obtained by modifying the polyimide with a modifying agent.

。也就是說，在本實施方式中，用來製造所述聚醯亞胺的二酐單體包括雙酚A型二醚二酐(4,4’-(4,4’-isopropylidenediphenoxy)bis(phthalic anhydride))(簡稱BPADA)，而用來製造所述聚醯亞胺的二胺單體包括間苯二胺(m-phenylenediamine，簡稱m-PDA)。在本實施方式中，前述聚醯亞胺可為市售品或經回收的聚醯亞胺粉體(亦即，二次料)，其中所述市售品例如是：由沙特基礎工業公司(Sabic)製造的ULTEM 9011紡絲級PEI、ULTEM 1010 PEI。在本實施方式中，前述聚醯亞胺的重量平均分子量介於約44000g/mol至約50000g/mol之間。 In this embodiment, the polyimide includes a repeating unit represented by the following formula I:

. That is, in this embodiment, the dianhydride monomer used to manufacture the polyimide includes bisphenol A type diether dianhydride (4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride)) (abbreviated as BPADA), and the diamine monomer used to manufacture the polyimide includes m-phenylenediamine (abbreviated as m-PDA). In this embodiment, the aforementioned polyimine may be a commercially available product or recycled polyimine powder (that is, a secondary material), wherein the commercially available product is, for example, produced by Saudi Basic Industries Corporation ( Sabic) ULTEM 9011 spinning grade PEI, ULTEM 1010 PEI. In this embodiment, the weight average molecular weight of the aforementioned polyimine is between about 44,000 g/mol and about 50,000 g/mol.

The solvent is not particularly limited, as long as it can dissolve the aforementioned polyimide. In this embodiment, the solvent may include N,N-dimethylacetamide (DMAc for short), N-methyl-2-pyrrolidone (NMP for short), or tetrahydrofuran. (tetrahydrofuran, referred to as THF). In addition, in this embodiment, the concentration of the aforementioned polyimine in the solvent may be between about 5 wt% and about 40 wt%.

In this embodiment, the modifier is represented by the following formula II: NH ₂ R formula II. In Formula II, R may be an aryl group having a carbon number of 6, an aralkyl group having a carbon number of 7 to 8, an alkoxyalkyl group having a carbon number of 2 to 6, or an alkyl group having a carbon number of 3 to 18. Specifically, in this embodiment, R can be selected from one of the groups represented by formula a to formula g:

，其中在式a至式g中，*表示鍵結位置。也就是說，在本實施方式中，改質劑可為苯胺、苯甲胺、苯乙胺、3-異丙氧基丙胺(3-isopropoxypropylamine，簡寫IPOPA)、異丙胺、正丁胺或十八胺(octadecylamine)。從另一觀點而言，在本實施方式中，改質劑可為在室溫和常壓下為液體的小分子胺類。

, Where in formula a to formula g, * represents the bonding position. That is to say, in this embodiment, the modifier can be aniline, benzylamine, phenethylamine, 3-isopropoxypropylamine (3-isopropoxypropylamine, abbreviated as IPOPA), isopropylamine, n-butylamine or octadecylamine. Amine (octadecylamine). From another point of view, in this embodiment, the modifier may be a small molecule amine that is liquid at room temperature and normal pressure.

In this embodiment, polyimide imine is represented by the following formula 1:

X

0.5。基於式1所示的結構可知，在本實施方式中，改質劑會與前述聚醯亞胺的醯亞胺基團進行反應，以使前述聚醯亞胺的醯亞胺基團開環。也就是說，在本實施方式中，以式1表示的聚醯胺醯亞胺為側鏈經改質的聚醯胺醯亞胺。在本實施方式中，前述聚醯亞胺與改質劑進行反應的反應溫度介於約30℃至約100℃之間，以及反應時間介於約4小時至約8小時之間。 Formula 1. In Formula 1, R is defined as described above for R in Formula II, and 0.02

X

0.5. Based on the structure shown in Formula 1, it can be seen that in this embodiment, the modifier reacts with the amide group of the aforementioned polyimine to open the ring of the aforementioned polyimine. That is, in this embodiment, the polyamide imide represented by Formula 1 is a polyamide imide whose side chain is modified. In this embodiment, the reaction temperature for the reaction between the polyimide and the modifier is between about 30° C. and about 100° C., and the reaction time is between about 4 hours and about 8 hours.

In this embodiment, the weight average molecular weight of the aforementioned polyamide imine is between about 47000 g/mol and about 55000 g/mol. On the other hand, in this embodiment, the ratio of the weight average molecular weight of the aforementioned polyimide to the weight average molecular weight of the aforementioned polyimine is between about 2.2 and about 2.6. In this embodiment, the viscosity of the solution containing the aforementioned polyimide is between about 1000 cps and about 10000 cps.

Next, please continue to refer to FIG. 1 and proceed to step S12, adding a non-solvent to the solution containing the polyimide, so that the polyimide is precipitated from the solution. Specifically, after the non-solvent is added to the solution containing the polyimide, the solvent of the polyimide solution and the non-solvent will be exchanged, so that the polyimide is solidified and precipitated. In this embodiment, the non-solvent may include methanol, ethanol, isopropanol, or water. In this embodiment, the polyamide imide precipitated from the solution is in the form of a solid powder.

After performing the above steps S10 to S12, the polyamide imide proposed in one embodiment of the present invention can be prepared. In this embodiment, the poly Amidoimines are represented by Formula 1 shown above, in which the definitions of R and X have been described in detail above, so they will not be repeated here. In addition, the relevant description of the polyimide imine has been described in detail in the foregoing, so it will not be repeated here.

It is worth noting that in this embodiment, the following steps are performed: the modifier represented by the above formula II is reacted with the polyimide represented by the above formula I to form a polyimide containing A solution, and adding a non-solvent to the solution, whereby the polyamide imide represented by the above formula 1 can be prepared. Furthermore, based on the structure shown in formula 1, it can be known that polyamide imines have a ring-opening structure (that is, side chains modified by modifiers) and the free volume of molecules increases, thereby polyamide imines The imine can have good hot workability and reduced hot work temperature.

In addition, in the embodiment of FIG. 1, the polyimide is prepared by performing steps S10 to S12, but the present invention is not limited to this. Hereinafter, other implementation types will be described with reference to FIG. 2. It must be noted here that the following embodiments follow the component symbols and part of the content of the foregoing embodiments, wherein the same or similar symbols are used to represent the same or similar components, and the description of the same technical content is omitted. For the description of the omitted parts, reference may be made to the foregoing embodiments, and the following embodiments will not be repeated.

Fig. 2 is a schematic flow chart of a preparation method of polyamideimines according to another embodiment of the present invention. Please refer to FIG. 2 and FIG. 1 at the same time. The preparation method shown in FIG. 2 is similar to the preparation method shown in FIG. 1, so the same or similar steps are represented by the same or similar symbols, and the description of the same technical content is omitted. For the description of the omitted parts, refer to the foregoing embodiment. Below, the preparation method shown in Figure 2 and The differences between the preparation methods shown in Figure 1 are explained.

Referring to FIG. 2, before performing step S12, the preparation method of this embodiment includes performing step S20, using a diluent to dilute the solution containing the polyamide imide represented by the above formula 1 to form the polyamide containing the aforementioned polyamide Diluted solution of amine imine.

The diluent is not particularly limited as long as it can dissolve the aforementioned polyamideimide. In this embodiment, the diluent may include N,N-dimethylacetamide (DMAc for short), N-methyl-2-pyrrolidone (NMP for short), or Tetrahydrofuran (tetrahydrofuran, THF for short).

In this embodiment, the viscosity of the solution containing the aforementioned polyimide before dilution is between about 1000 cps to about 10,000 cps, and the viscosity of the diluted solution containing the aforementioned polyimide is between about 10 cps to about 10 cps. Between about 200cps.

Hereinafter, the features of the present invention will be described in more detail with reference to Examples 1 to 14 and Comparative Example 1. Although the following embodiments are described, the materials used, their amounts and ratios, processing details, processing procedures, etc. can be appropriately changed without going beyond the scope of the present invention. Therefore, the embodiments described below should not restrictively interpret the present invention.

Example 1

First, 100 parts by weight of polyimide (manufactured by Sabic, trade name: ULTEM 1010 PEI) is placed in the solvent DMAc. Dissolve to form a 25wt% polyimide solution. Next, 5 parts by weight of modifier aniline was added to the polyimide solution and reacted at 80° C. for 6 hours to form a solution containing the polyimide imine of Example 1, wherein the polyimide The molar ratio with the modifier aniline is 1:25.7, and the viscosity of the solution containing the polyimide imine of Example 1 is about 10000 cps. Subsequently, the diluent DMAc was used to dilute the solution containing the polyimide imide of Example 1 to form a diluted solution containing the polyimide imide of Example 1, wherein the viscosity of the diluted solution was about 100cps. Next, 2 liters (or excess) of non-solvent methanol was added to the diluted solution to precipitate the polyamide imine of Example 1. It is worth noting that the precipitated polyamide imide of Example 1 will undergo a filtration and drying step for subsequent use.

Example 2

First, 100 parts by weight of polyimide (manufactured by Sabic, trade name: ULTEM 1010 PEI) was dissolved in the solvent DMAc to form a 25 wt% polyimide solution. Next, 1.5 parts by weight of the modifier benzylamine was added to the polyimide solution, and the reaction was carried out at 80°C for 6 hours to form a solution containing the polyimide imine of Example 2, wherein the polyimide The molar ratio of imine to modifier benzylamine is 1:6.7, and the viscosity of the solution containing the polyimide imine of Example 2 is about 7300 cps. Subsequently, the diluent DMAc was used to dilute the solution containing the polyamide imide of Example 2 to form a diluted solution containing the polyamide imide of Example 2, wherein the viscosity of the diluted solution was about 100cps. After that, 2 liters (or excess) of non-solvent methanol was added to the diluted solution In this way, the polyimide of Example 2 was precipitated. It is worth noting that the precipitated polyamide imide of Example 2 will undergo a filtration and drying step for subsequent use.

Example 3

First, 100 parts by weight of polyimide (manufactured by Sabic, trade name: ULTEM 1010 PEI) was dissolved in the solvent DMAc to form a 25 wt% polyimide solution. Next, 2 parts by weight of the modifier benzylamine was added to the polyimide solution, and the reaction was carried out at 80° C. for 6 hours to form a solution containing the polyimide imide of Example 3, wherein the polyimide The molar ratio of imine to modifier benzylamine is 1:8.9, and the viscosity of the solution containing the polyimide imine of Example 3 is about 4400 cps. Subsequently, the diluent DMAc was used to dilute the solution containing the polyamide imide of Example 3 to form a diluted solution containing the polyamide imide of Example 3, wherein the viscosity of the diluted solution was about 100cps. After that, 2 liters (or excess) of non-solvent methanol was added to the diluted solution to precipitate the polyamide imine of Example 3. It is worth noting that the precipitated polyamide imide of Example 3 will undergo a filtration and drying step for subsequent use.

Example 4

First, 100 parts by weight of polyimide (manufactured by Sabic, trade name: ULTEM 1010 PEI) was dissolved in the solvent DMAc to form a 25 wt% polyimide solution. Next, 5 parts by weight of the modifier phenethylamine was added to the polyimide solution, and the reaction was carried out at 80°C for 6 hours, To form a solution containing the polyimide of Example 4, wherein the molar ratio of the polyimide to the modifier phenethylamine is 1:19.8, and the solution containing the polyimide of Example 4 The viscosity is about 1000cps. Subsequently, the diluent DMAc was used to dilute the solution containing the polyamide imide of Example 4 to form a diluted solution containing the polyamide imide of Example 4, wherein the viscosity of the diluted solution was about 100cps. After that, 2 liters (or excess) of non-solvent methanol was added to the diluted solution to precipitate the polyamide imine of Example 4. It is worth noting that the precipitated polyamide imide of Example 4 will undergo a filtration and drying step for subsequent use.

Example 5

First, 100 parts by weight of polyimide (manufactured by Sabic, trade name: ULTEM 1010 PEI) was dissolved in the solvent DMAc to form a 25 wt% polyimide solution. Next, 1.1 parts by weight of the modifier 3-isopropoxypropylamine was added to the polyimide solution, and the reaction was carried out at 80° C. for 6 hours to form a solution containing the polyimide imine of Example 5. , Wherein the molar ratio of the polyimide to the modifier 3-isopropoxypropylamine is 1:4.5, and the viscosity of the solution containing the polyimide imide of Example 5 is about 9300 cps. Subsequently, the diluent DMAc was used to dilute the solution containing the polyimide imide of Example 5 to form a diluted solution containing the polyimide imide of Example 5, wherein the viscosity of the diluted solution was about 100cps. After that, 2 liters (or excess) of non-solvent methanol was added to the diluted solution to precipitate the polyamide imine of Example 5. It is worth noting that the precipitated polyamide imide of Example 5 will undergo a filtration and drying step. To facilitate subsequent use.

Example 6

First, 100 parts by weight of polyimide (manufactured by Sabic, trade name: ULTEM 1010 PEI) was dissolved in the solvent DMAc to form a 25 wt% polyimide solution. Next, 2 parts by weight of the modifier 3-isopropoxypropylamine was added to the polyimide solution, and the reaction was carried out at 80° C. for 6 hours to form a solution containing the polyimide imine of Example 6. , Wherein the molar ratio of polyimide to modifier 3-isopropoxypropylamine is 1:8.2, and the viscosity of the solution containing polyimide of Example 6 is about 7800 cps. Subsequently, the diluent DMAc was used to dilute the solution containing the polyamide imide of Example 6 to form a diluted solution containing the polyamide imide of Example 6, wherein the viscosity of the diluted solution was about 100cps. After that, 2 liters (or excess) of non-solvent methanol was added to the diluted solution to precipitate the polyamide imine of Example 6. It is worth noting that the precipitated polyamide imide of Example 6 will undergo a filtration and drying step for subsequent use.

Example 7

First, 100 parts by weight of polyimide (manufactured by Sabic, trade name: ULTEM 1010 PEI) was dissolved in the solvent DMAc to form a 25 wt% polyimide solution. Next, 5 parts by weight of the modifier 3-isopropoxypropylamine was added to the polyimide solution, and the reaction was carried out at 80°C 6 hours to form a solution containing the polyimide imine of Example 7, wherein the molar ratio of the polyimine to the modifier 3-isopropoxypropylamine was 1:20.5, and the polyimide contained the polyimide of Example 7. The viscosity of the solution of amide imine is about 2000 cps. Subsequently, the diluent DMAc was used to dilute the solution containing the polyimide imide of Example 7 to form a diluted solution containing the polyimide imide of Example 7, wherein the viscosity of the diluted solution was about 100cps. After that, 2 liters (or excess) of non-solvent methanol was added to the diluted solution to precipitate the polyamide imine of Example 7. It is worth noting that the precipitated polyamide imide of Example 7 will undergo a filtration and drying step for subsequent use.

Example 8

First, 100 parts by weight of polyimide (manufactured by Sabic, trade name: ULTEM 1010 PEI) was dissolved in the solvent DMAc to form a 25 wt% polyimide solution. Next, 1.1 parts by weight of the modifier n-butylamine was added to the polyimide solution, and the reaction was carried out at 80°C for 6 hours to form a solution containing the polyimide imine of Example 8, wherein the polyimide The molar ratio of imine to modifier n-butylamine is 1:7.2, and the viscosity of the solution containing the polyamide imine of Example 8 is about 8500 cps. Subsequently, the diluent DMAc was used to dilute the solution containing the polyimide imide of Example 8 to form a diluted solution containing the polyimide imide of Example 8, wherein the viscosity of the diluted solution was about 100cps. After that, 2 liters (or excess) of non-solvent methanol was added to the diluted solution to precipitate the polyamide imine of Example 8. It is worth noting that after precipitation The polyimide imine of Example 8 will be filtered and dried to facilitate subsequent use.

Example 9

First, 100 parts by weight of polyimide (manufactured by Sabic, trade name: ULTEM 1010 PEI) was dissolved in the solvent DMAc to form a 25 wt% polyimide solution. Next, 2 parts by weight of the modifier n-butylamine was added to the polyimide solution, and the reaction was carried out at 80°C for 6 hours to form a solution containing the polyimide imine of Example 9, wherein the polyimide The molar ratio of imine to modifier n-butylamine is 1:13.1, and the viscosity of the solution containing the polyamide imine of Example 9 is about 6900 cps. Subsequently, the diluent DMAc was used to dilute the solution containing the polyimide imide of Example 9 to form a diluted solution containing the polyimide imide of Example 9, wherein the viscosity of the diluted solution was about 100cps. After that, 2 liters (or excess) of non-solvent methanol was added to the diluted solution to precipitate the polyamide imine of Example 9. It is worth noting that the precipitated polyamide imide of Example 9 will undergo a filtration and drying step for subsequent use.

Example 10

First, 100 parts by weight of polyimide (manufactured by Sabic, trade name: ULTEM 1010 PEI) was dissolved in the solvent DMAc to form a 25 wt% polyimide solution. Next, 5 parts by weight of the modifier n-butylamine was added to the polyimide solution, and the reaction was carried out at 80°C for 6 hours to form a solution containing the polyimide of Example 10, wherein the polyimide Imines and changes The molar ratio of the mass agent n-butylamine is 1:32.8, and the viscosity of the solution containing the polyimide imine of Example 10 is about 3000 cps. Subsequently, the diluent DMAc was used to dilute the solution containing the polyamide imide of Example 10 to form a diluted solution containing the polyamide imide of Example 10, wherein the viscosity of the diluted solution was about 100cps. After that, 2 liters (or excess) of non-solvent methanol was added to the diluted solution to precipitate the polyamide imine of Example 10. It is worth noting that the precipitated polyamide imide of Example 10 will undergo a filtration and drying step for subsequent use.

Example 11

First, 100 parts by weight of polyimide (manufactured by Sabic, trade name: ULTEM 1010 PEI) was dissolved in the solvent DMAc to form a 25 wt% polyimide solution. Next, 2 parts by weight of the modifier isopropylamine was added to the polyimide solution, and the reaction was carried out at 80°C for 6 hours to form a solution containing the polyimide imide of Example 11, wherein the polyimide The molar ratio of the amine to the modifier isopropylamine is 1: 16.2, and the viscosity of the solution containing the polyimide imine of Example 11 is about 4410 cps. Subsequently, the diluent DMAc was used to dilute the solution containing the polyimide imide of Example 11 to form a diluted solution containing the polyimide imide of Example 11, wherein the viscosity of the diluted solution was about 100cps. After that, 2 liters (or excess) of non-solvent methanol was added to the diluted solution to precipitate the polyamide imine of Example 11. It is worth noting that the precipitated polyamide imide of Example 11 will undergo a filtration and drying step for subsequent use.

Example 12

First, 100 parts by weight of polyimide (manufactured by Sabic, trade name: ULTEM 1010 PEI) was dissolved in the solvent DMAc to form a 25 wt% polyimide solution. Next, 5 parts by weight of the modifier isopropylamine was added to the polyimide solution, and the reaction was carried out at 80° C. for 6 hours to form a solution containing the polyimide imine of Example 12, wherein the polyimide The molar ratio of the amine to the modifier isopropylamine was 1:40.6, and the viscosity of the solution containing the polyimide imine of Example 12 was about 3500 cps. Subsequently, the diluent DMAc was used to dilute the solution containing the polyimide imide of Example 12 to form a diluted solution containing the polyimide imide of Example 12, wherein the viscosity of the diluted solution was about 100cps. After that, 2 liters (or excess) of non-solvent methanol was added to the diluted solution to precipitate the polyamide imine of Example 12. It is worth noting that the precipitated polyamide imide of Example 12 will undergo a filtration and drying step for subsequent use.

Example 13

First, 100 parts by weight of polyimide (manufactured by Sabic, trade name: ULTEM 1010 PEI) was dissolved in the solvent DMAc to form a 25 wt% polyimide solution. Next, 1 part by weight of modifier stearylamine was added to the polyimide solution, and the reaction was carried out at 80°C for 6 hours to form a solution containing the polyimide imide of Example 13, wherein the polyimide The molar ratio of imine to modifier stearylamine is 1:1.8, and the viscosity of the solution containing the polyimide imine of Example 13 is about 9000 cps. Then, use the diluent DMAc to implement The polyamideimide solution of Example 13 was diluted to form a diluted solution containing the polyamideimide of Example 13, wherein the viscosity of the diluted solution was about 100 cps. After that, 2 liters (or excess) of non-solvent methanol was added to the diluted solution to precipitate the polyamide imine of Example 13. It is worth noting that the precipitated polyamide imide of Example 13 will undergo a filtration and drying step for subsequent use.

Example 14

First, 100 parts by weight of polyimide (manufactured by Sabic, trade name: ULTEM 1010 PEI) was dissolved in the solvent DMAc to form a 25 wt% polyimide solution. Next, 2 parts by weight of the modifier stearylamine was added to the polyimide solution, and the reaction was carried out at 80° C. for 6 hours to form a solution containing the polyimide imide of Example 14, wherein the polyimide The molar ratio of imine to modifier octadecylamine is 1:3.6, and the viscosity of the solution containing the polyimide imine of Example 14 is about 7100 cps. Subsequently, the diluent DMAc was used to dilute the solution containing the polyimide imide of Example 14 to form a diluted solution containing the polyimide imide of Example 14, wherein the viscosity of the diluted solution was about 100cps. After that, 2 liters (or excess) of non-solvent methanol was added to the diluted solution to precipitate the polyamide imine of Example 14. It is worth noting that the precipitated polyamide imide of Example 14 will undergo a filtration and drying step for subsequent use.

Comparative example 1

In Comparative Example 1, the modifier to polyimide (made by Saudi Arabia Made by Sabic, trade name: ULTEM 1010 PEI) for modification. That is, in Comparative Example 1, ULTEM 1010 PEI, a commercial product of polyimide, was used as it was.

_{Afterwards, the glass transition temperature (Tg), 10% thermogravimetric loss temperature (T d10%} ), viscosity (η _inh ), and the glass transition temperature (Tg), 10% thermogravimetric loss temperature (T d10% ), viscosity (η inh) of the polyamide imide of Examples 1-14 and the ULTEM 1010 PEI of Comparative Example 1 were carried out respectively. Measurement of melt index (MI) and contact angle. The description of the aforementioned measurement items is as follows, and the measurement results are shown in Table 1.

<Measurement of glass transition temperature (Tg)>

A thermomechanical analyzer (manufactured by Maia, model: DSC200 F3) was used to set the polyamide imide of Examples 1-14 and the ULTEM 1010 PEI of Comparative Example 1 to 10 in a nitrogen environment and a heating rate. The glass transition temperature (°C) is measured under the condition of °C/min.

<10% thermogravimetric loss temperature (T _d10% ) Measurement>

A thermogravimetric analyzer (manufactured by TA Instruments, model: Q50) was used to set the polyamide imide of Examples 1-14 and the ULTEM 1010 PEI of Comparative Example 1 in a nitrogen atmosphere and the heating rate to 20°C/min. Measure and record the weight change of each polyamideimide and ULTEM 1010 PEI under the conditions of, wherein the measured temperature when each polyamideimide and ULTEM 1010 PEI lose 10% of the weight is 10% Thermogravimetric loss temperature (℃).

<Viscosity (η _inh ) Measurement>

The polyamide imide of Examples 1-14 and the ULTEM 1010 PEI of Comparative Example 1 were dissolved in the solvent DMAc to form a solution with a concentration of 0.5 g/dL, and the temperature was set to 30 ℃ for each solution. Measurement of viscosity (dL/g).

<Measurement of Melt Index (MI)>

Measure the melt index (g/10min) of the polyamide imide of Examples 1-14 and the ULTEM 1010 PEI of Comparative Example 1 according to ASTM D-1238. The weight load is 5Kg, and the test temperature is based on The test samples used are different, please refer to Table 1 for detailed test temperature. Generally speaking, the higher the melt index, the better the hot workability and the better the thermal fluidity.

<Measurement of contact angle>

Water was dropped on the polyamide imide of Examples 1-14 and ULTEM 1010 PEI of Comparative Example 1, respectively. After the water no longer flows, use a contact angle measuring device (Model: Model TK-C1380U, manufactured by JVC Corporation) to measure the contact angles (degrees) between the water and each polyimide and ULTEM 1010 PEI respectively.

From Table 1 above, it can be seen that the polyamide imide of Examples 1-14 and the ULTEM 1010 PEI of Comparative Example 1 have similar glass transition temperatures and similar 10% thermogravimetric loss temperatures. This result shows that the polyimide represented by the above formula 1 obtained by modifying the polyimide represented by the above formula I by the modifier represented by the above formula II of the present invention is different from the unmodified polyimide represented by the above formula 1 The quality polyimide has similar thermal properties.

From Table 1 above, it can be seen that the polyamide imide of Examples 1-14 and the ULTEM 1010 PEI of Comparative Example 1 have similar viscosities. This result shows that the polyimide represented by the above formula I is modified by the modifier represented by the above formula II, and the degree of polymerization of the resultant product (that is, the polyimide represented by the above formula 1) Not affected.

It can be seen from Table 1 above that compared with the melt index and thermal processing temperature of the unmodified ULTEM 1010 PEI of Comparative Example 1, the polyimide imines of Examples 1-14 can be processed at a lower thermal processing temperature. Has better fluidity. This result shows that the polyimide represented by the above formula 1 obtained by modifying the polyimide represented by the above formula I by the modifier represented by the above formula II of the present invention has good thermal properties. Processability, good thermal fluidity and reduced thermal processing temperature.

From Table 1 above, it can be seen that compared with the unmodified ULTEM 1010 of Comparative Example 1 Compared with the contact angle of PEI, the polyimidimines of Examples 1-14 have a smaller contact angle. This result shows that compared with unmodified polyimide, the polyimide of the present invention is obtained by modifying the polyimide represented by the above formula I by the modifier represented by the above formula II. The polyimide represented by 1 is relatively hydrophilic.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field can make some changes and modifications without departing from the spirit and scope of the present invention. The scope of protection of the present invention shall be determined by the scope of the attached patent application.

S10, S12: steps

Claims (10)

A preparation method of polyimide, comprising: reacting a modifier with polyimide dissolved in a solvent to form a first solution containing polyimide, wherein the polyimide the reaction temperature of the reaction with the modifier is between 30 ^o C to 100 ^o C, the reaction time lies between 4 hours to 8 hours, said polyimide comprising a repeating unit represented by the following formula I , The modifier is represented by the following formula II, and the polyamide imine is represented by the following formula 1:

Formula I NH ₂ R Formula II

Formula 1, wherein the weight average molecular weight of the polyimine is between 44000 g/mol and 50000 g/mol; R is an aryl group with a carbon number of 6, an aralkyl group with a carbon number of 7 to 8, and Alkoxyalkyl having 2 to 6 or alkyl having 3 to 18; and 0.02≤X≤0.5; and adding a non-solvent to the first solution containing the polyimide , So that the polyamide imine precipitates out from the first solution. The method for preparing polyamideimine as described in item 1 of the scope of patent application, wherein the modifier is selected from the group consisting of aniline, benzylamine, phenethylamine, 3-isopropoxypropylamine, isopropylamine, normal One of the group consisting of butylamine and stearylamine. According to the method for preparing polyamideimide described in item 1 of the scope of the patent application, the weight average molecular weight of the polyamideimide is between 47000 g/mol and 55000 g/mol. The preparation method of polyamideimide as described in item 1 of the scope of patent application, wherein the solvent includes N,N-dimethylacetamide (DMAc) and N-methylpyrrolidone Or tetrahydrofuran. The method for preparing polyamidoimines as described in item 1 of the scope of patent application, wherein the non-solvent includes methanol, ethanol, isopropanol or water. As described in item 1 of the scope of the patent application, the preparation method of polyimide further comprises: before adding the non-solvent to the first solution containing the polyimide imine, diluting The agent dilutes the first solution containing the polyimide to form a second solution containing the polyimide. The method for preparing polyimide imine as described in item 6 of the scope of the patent application, wherein the viscosity of the first solution containing the polyimide imine is between 1000 cps and 10000 cps, and contains The viscosity of the second solution of the polyimide is between 10 cps and 200 cps. The preparation method of polyamideimide as described in item 6 of the scope of patent application, wherein the diluent contained therein includes N,N-dimethylacetamide, N-methylpyrrolidone or tetrahydrofuran. The preparation method of polyimide as described in the first item of the scope of patent application, wherein the ratio of the weight average molecular weight of the polyimide to the weight average molecular weight of the polyimide is between 2.2 to Between 2.6. According to the method for preparing polyimidimines as described in item 1 of the scope of the patent application, the concentration of the polyimines in the solvent is between 5 wt% and 40 wt%.

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