KR19990070420A - Orthopedic Water Resistant Polyurethane Casting Sheet - Google Patents

Abstract

The present invention improves lubricity and additionally supports defoaming properties by using a new compound siloxane-polyethyleneglycol copolymer in a hydrocurable urethane prepolymer in an orthopedic hydrocurable polyurethane casting sheet. Orthopedic hydrocurable poly that is made to disperse the lubricity of the copolymer evenly on the surface of the casting sheet by adding sodium alkylethersulfate as a lubricant dispersant to the polyurethane prepolymer together with the copolymer. Urethane casting sheet.

Description

Orthopedic Water Resistant Polyurethane Casting Sheet

FIELD OF THE INVENTION The present invention relates to orthopedic hydrocurable polyurethane casting sheets, and more particularly to cast sheets comprising orthopedic hydrocurable polyurethane prepolymers having both high lubricity and increased antifoaming properties. .

Another object of the present invention is to distribute the lubricity evenly on the surface of the casting sheet.

In general, orthopedic surgeons have mainly used gypsum bandages to fix fractures. However, gypsum bandages are excessive in weight, not easy to distribute air, are inadequate for X-ray imaging, weak in strength when in contact with moisture, and damage to the patient's skin by the growth of microorganisms.

In order to overcome the drawbacks of the gypsum bandage as described above, a casting sheet coated with a knitted polyurethane sheet in a knitted fabric sheet has been recently used.

These casting sheets are used for the fracture sites of patients after being immersed in water for a period of time in the same way as gypsum bandages, and water begins to cure the polyurethane prepolymers that are coated on the knitted fabric sheet, After hardening, it hardens to fix the fracture.

However, when the casting sheet is treated, there is inconvenience in the procedure due to excessive adhesive force of the prepolymer, and a manufacturing method of the casting sheet for removing such inconvenience is disclosed in US Pat. No. 4,774,937. However, according to the method as described above, the slippery phenomenon occurs during the procedure to remove the inconvenience in the procedure, but there was a problem that the strength of the casting sheet is lowered due to the generation of bubbles.

In order to solve the problems of the prior art as described above, in the present invention, a siloxane-polyethylene glycol copolymer, which is a new compound, is used in a hydrocurable polyurethane prepolymer, thereby improving lubricity and additionally supporting defoaming. have.

In addition, the present invention by using sodium alkylethersulfate as a lubricant dispersant in the polyurethane prepolymer with the copolymer in order to distribute the lubricity of the copolymer evenly on the surface of the casting sheet.

The above sodium alkyl ether sulfate was found to have a surprising phenomenon that when used with the copolymer of the present invention shows a lubricity dispersing effect, but when used with other lubricants shows little lubricity dispersion effect.

One object of the present invention relates to a compound of the general formula (I) below and a method for preparing the compound as a new lubricant.

Synthesis of Formula (I) is prepared by reacting an alkoxysiloxane of Formula (II) with a polyol of Formula (III) by using an ester exchange reaction as follows. At this time, titanium tetraisopropoxide (titanium tetraisopropoxide: [(CH ₃ ) ₂ CHO] ₄ Ti) is used.

R ₁ , R ₂ : alkyl, aryl, aralkyl or unsaturated alkyl, alkoxy

R ₃ : alkyl or hydrogen

R ₄ : methoxy or

R ₅ : Or hydrogen

m is an integer 10-200, n is an integer 1-20.

In the synthesis sequence, the polyol of the general formula (III) is put into a synthetic container equipped with a heater, a stirrer, a condenser, and heated to melt. While stirring the molten polyol of the general formula (III), the siloxane compound of the general formula (II) was added and mixed well. Then, a titanium tetraisopropoxide catalyst was added to the internal temperature of 1 ° C./min. To 6 ° C./min. . Heat at speed and take the methanol generated at the condenser. The pressure in the reaction vessel is maintained at 1 atm throughout the entire reaction process.

When the internal temperature is 125 ° C ~ 130 ° C, the heating is stopped, and the temperature is kept constant, the mixture is stirred for about 1 hour, the product is taken out of the synthesis vessel, cooled slowly at 15 ° C to 39 ° C, and the obtained crystal is 100 mesh or less. Grind to powder and use as lubricant.

Next, another object of the present invention is to prepare a casting sheet made of a hydrocurable prepolymer. Humidity in the whole manufacturing process is always maintained at a relative humidity of 0.51% or less (room temperature 32 ° C., 0.172 g moisture / m 3 air).

As raw material of urethane resin, diisocyanate compounds such as diphenylmethanediisocya-nate or toluenediisocyanate, polyol compounds such as polyetherdiol and polyethertriol, and urethane resin flow inhibitors The polysiloxane compound as a phosphorus silicon dioxide and an antifoaming agent is placed in a reaction vessel and mixed with sufficient stirring at 15 ° C. to 39 ° C., and then the internal temperature is increased until the internal temperature of the container is 80 ° C. to 95 ° C. The mixture is heated and stirred at a rate of 0.5 ° C./min. To 5 ° C./min. When the internal temperature rises to 80 ° C to 95 ° C, the heating is stopped, and the internal temperature is immediately cooled by a hot bath at a rate of 0.2 ° C / min. To 1 ° C / min. When the internal temperature was cooled to 65 ° C to 75 ° C, the cooling was stopped and the internal temperature was dropped at a rate of 0.2 ° C / min.-1.3 ° C / min. While stirring by adding a lubricant of formula (I). When the internal temperature drops to 55 ° C to 60 ° C, the reaction vessel is sealed and the internal temperature is cooled at 0.05 ° C / min. To 0.3 ° C / min. When the internal temperature is 30 ℃ ~ 45 ℃ stop cooling, add a hydrocurable reaction catalyst such as dimorpholinodiethylether (DMDEE), stir and mix thoroughly, urethane, such as methane sulfonic acid (MSA) A resin stabilizer is further added and stirred.

The synthesized hydrocurable polyurethane prepolymer is applied at 37% to 45% by weight on a glass fiber knitted fabric. The coating amount is expressed by the following equation.

A: 20 cm long casting sheet weight coated with prepolymer

B: Weight of residue remaining after incineration of A.

Next, another object of the present invention is to prepare a hydrocurable prepolymer casting sheet containing a sodium alkyl ether sulfate lubricating dispersant. Humidity in the whole manufacturing process is always kept below 0.51% of relative humidity (room temperature 32 ° C., 0.172 g moisture / m 3 air).

As a urethane resin raw material, a diisocyanate compound such as diphenylmethane diisocyanate or toluene diisocyanate, a polyol compound such as polyetherdiol and polyethertriol, silicon dioxide as a urethane resin flow inhibitor, and a polysiloxane compound as an antifoaming agent are contained in a reaction vessel. The mixture is stirred and mixed sufficiently at a temperature of 39 ° C. to 39 ° C., and the internal temperature is 0.5 ° C./min until the internal temperature of the container is 80 ° C. to 95 ° C. The mixture is heated and stirred at a rate of ˜5 ° C./min. When the internal temperature rose to 80 ° C to 95 ° C, the heating was stopped and the internal temperature was immediately set to 0.2 ° C / min. Cool the bath at ~ 1 ° C / min. When the internal temperature is cooled to 65 ℃ ~ 75 ℃ stop the cooling and add the sodium alkyl ether sulfate, a lubricant and lubricating dispersant, while stirring and the internal temperature is reduced to 0.2 ℃ / min ~ 1.3 ℃ / min. When the internal temperature drops to 55 ℃ ~ 60 ℃, seal the reaction vessel and cool it internally at 0.05 ℃ / min. ~ 0.3 ℃ / min. When the internal temperature is 30 ℃ ~ 45 ℃ stop cooling, add a hydrocurable reaction catalyst such as DMDEE and stir thoroughly, and then add a urethane resin stabilizer such as MSA and stir.

The synthesized hydrocurable polyurethane prepolymer is applied at 37% to 45% by weight on a glass fiber knitted fabric. The coating amount is expressed by the following equation.

A: 20 cm long casting sheet weight coated with prepolymer

B: weight of residue remaining after incineration of A

Example 1

Synthesis of siloxane-polyethylene glycol copolymer

840 g (0.1 mol) of polyethylene glycol (Polyeth-yleneglycol, PEG-6000 of Korea Polyol) was placed in a synthetic container equipped with a heater, a stirrer, and a condenser, and the internal temperature was maintained at 65 ° C or higher.

While stirring the melted polyethylene glycol, when the internal temperature is 80 ° C, methoxy terminal dimethylphenylsiloxane (Dimethylphenylsiloxane, methoxy-terminated, INTERMEDIATE 3037) of Dow Corning, USA, 27.35g (0.15mol) is added to mix well, and then the titanium tetra 0.52 g of isopropoxide was added, and then the internal temperature was raised at a rate of 1 ° C./min. And methanol generated at this time was taken into a condenser. The pressure in the reaction vessel was maintained at 1 atm throughout the entire reaction process.

When the internal temperature is 127.5 ° C. (± 2.5 ° C.), the heating is stopped and the internal temperature is kept constant at 127.5 ° C. (± 2.5 ° C.), followed by stirring for 50 minutes. The product is removed from the synthesis vessel, and then cooled slowly and crystallized at 20 ° C. Got. It was ground to a powder of 100 mesh or less and used as a lubricant.

Example 2

Preparation of Orthopedic Hydrosetting Polyurethane Casting Sheet

557.7 g of diphenylmethanediisocyanate (ISONATE 2143 LK from Dow Chemical, USA), 300 g of polypropyleneglycol, KONIX PP-1000 from Polyol Korea, Glyce-rine started polypropyleneglycol, ARCOL from USA LG-650) 34.52g, 10.13g of silicon dioxide as urethane resin flow inhibitor, 10g of polydimethylsiloxane (Antifoam-A) from Dow Corning, USA Was stirred while heating at a rate of 1.08 ° C./min. When the internal temperature was 90 ° C., the heating was stopped, the reaction vessel was sealed, and the internal temperature was cooled at 0.4 ° C./min.

When the reaction vessel was cooled to 68 ° C., the cooling was stopped and 44.61 g of siloxane-polyethyleneglycol copol-ymer prepared in Example 1 was added as a lubricant, and the internal temperature was 1.0 ° C./min. Dropped into. When the internal temperature dropped to 60 ° C., the reaction vessel was sealed, and the internal temperature was cooled by hot water at a rate of 0.1 ° C./min.

When the internal temperature was 42 ° C, cooling was stopped and 15.79 g of DMDEE was added as a hydrocuring reaction catalyst. The mixture was stirred until uniformly mixed. Then, 0.48 g of MSA was added to the container as a urethane resin stabilizer, followed by stirring. 970.1 g were obtained.

Humidity was kept below 0.51% relative humidity (room temperature 32 ° C, 0.172g moisture / m 3 air) throughout the entire reaction process.

The prepared prepolymer was applied onto a glass fiber knitted fabric to make a casting sheet. At this time, the coating amount of the prepolymer on the casting sheet was 40.2%. The application amount is expressed by the following equation.

A: 20 cm long casting sheet weight coated with prepolymer

B: Weight of residue remaining after incineration of A.

Example 3

Preparation of Orthopedic Hydrocurable Polyurethane Casting Sheet with Lubricant Dispersant

557.7 g of diphenylmethanediisocyanate (ISONATE 2143 LK from Dow Chemical, USA), 300 g of polypropyleneglycol, KONIX PP-1000 from Polyol Korea, Glycerine started polypropylenegycol, LG- from ARCOL, USA 650) 34.52g, 10.13g of silicon dioxide as a urethane resin flow inhibitor, 10g of polydimethylsiloxane (ANTIFOAM-A, Dow Corning, USA) as a defoaming agent and stirred, and then supplied a 100 ℃ of a bath solution to give an internal temperature of 108 It stirred, heating at the rate of ° C / min. When the internal temperature was 90 ° C., the heating was stopped, the reaction vessel was sealed, and the internal temperature was cooled at 0.4 ° C./min.

When the reaction vessel was cooled to 68 ° C., the cooling was stopped, and 44.61 g of the siloxane-polyethylene glycol polymer prepared in Example 1 and 1.784 g of dried sodium laurylethersulfate were added as a lubricant. It dropped at the rate of 1.0 degree-C / min. When the internal temperature dropped to 60 ° C., the reaction vessel was sealed, and the internal temperature was cooled by hot water at a rate of 0.1 ° C./min.

When the internal temperature was 42 ° C, the cooling was stopped and 15.79 g of DMDEE was added as a hydrocuring reaction catalyst. The mixture was stirred until evenly mixed. Then, 0.48 g of MSA was added to the container as a urethane resin stabilizer. 973.5 g were obtained.

Humidity in the reaction was maintained below 0.51% relative humidity (room temperature 32 ° C., 0.172 g moisture / m 3 air) throughout the entire reaction process.

The prepared prepolymer was applied onto a glass fiber knitted fabric to make a casting sheet. At this time, the coating amount of the prepolymer on the casting sheet was 40.2%. The application amount is expressed by the following equation.

A: 20 cm long casting sheet weight coated with prepolymer

B: Weight of residue remaining after incineration of A.

Example 4

Preparation of Orthopedic Hydrocurable Polyurethane Prepolymer without Defoamer

557.7g of diphenylmethanediisocyanate (ISONATE 2143 LK from Dow Chemical, USA) and 300g of polypropyleneglycol (KONIX PP-1000 from Polyol, Korea) 650) 34.52 g, 10.13 g of silicon dioxide as a urethane resin flow inhibitor was mixed and stirred, and then supplied with a 100 ° C. hot water solution and stirred while heating the internal temperature at a rate of 1.08 ° C./min. When the internal temperature was 90 ° C., the heating was stopped, the reaction vessel was sealed, and the internal temperature was cooled at 0.4 ° C./min.

When the reaction vessel was cooled to 68 ° C., the cooling was stopped and 44.16 g of the siloxane-polyethylene glycol copolymer prepared in Example 1 was added as a lubricant and the internal temperature was dropped at a rate of 1.0 ° C./min while stirring. When the internal temperature dropped to 60 ° C., the reaction vessel was sealed, and the internal temperature was cooled by hot water at a rate of 0.1 ° C./min.

When the internal temperature was 42 ° C, cooling was stopped and 15.79 g of DMDEE was added as a hydrocuring reaction catalyst. The mixture was stirred until uniformly mixed. Then, 0.48 g of MSA was added to the container as a urethane resin stabilizer, followed by stirring. 970.1 g were obtained.

Humidity in the reaction was kept below 0.51% relative humidity (room temperature 32 ℃, 0.172g moisture / ㎥ air) throughout the reaction.

Comparative Example 1

A casting sheet was prepared in the same manner as in Example 2, except that 44.61 g of PLURONIC ™ F108, manufactured by BASF Wyandote, was used instead of the product of Example 1, which was used as a lubricant in Example 3.

Comparative Example 2

557.7g of diphenylmethanediisocyanate (ISONATE 2143 LK from Dow Chemical, USA) and 300g of polypropyleneglycol (KONIX PP-1000 from Polyol, Korea) 650) 34.52 g, 10.13 g of silicon dioxide as a urethane resin flow inhibitor was mixed and stirred, and then supplied with a 100 ° C. hot water solution and stirred while heating the internal temperature at a rate of 1.08 ° C./min. When the internal temperature was 97 ° C., the heating was stopped, the reaction vessel was sealed, and the internal temperature was cooled at 0.4 ° C./min.

When the reaction vessel was cooled to 68 ° C., cooling was stopped and the internal temperature was dropped to 1.0 ° C./min. When the internal temperature dropped to 60 ° C., the reaction vessel was sealed, and the internal temperature was cooled by hot water at a rate of 0.1 ° C./min.

When the internal temperature was 42 ° C, cooling was stopped and 15.79 g of DMDEE was added as a hydrocuring reaction catalyst. The mixture was stirred until uniformly mixed. Then, 0.48 g of MSA was added to the container as a urethane resin stabilizer, followed by stirring. 970.1 g were obtained.

Humidity in the reaction was maintained below 0.51% relative humidity (room temperature 32 ° C., 0.172 g moisture / m 3 air) throughout the entire reaction process.

[Test Items and Methods]

1. Lubricity test

Immediately after opening each casting sheet prepared in Examples 2, 3, and Comparative Example 1 in a wrapping paper, the casting sheet was immersed in water at 20 ° C. to 25 ° C. for 15 seconds, taken out, shaken out vigorously, and shaken off the moisture. Is placed on the floor with a length of 50cm, and a sliding weight of 200g in weight, 5cm in length and 5cm in height is placed on it, and the moving force is 50kgf load cell when the distance is moved for 1 minute and 50 seconds at a speed of 15cm / min. Measure with a tester or a spring balance.

2. Defoaming Test

The polyurethane prepolymers prepared by Examples 2, 4, Comparative Example 1, and Comparative Example 2 were applied on a glass substrate in a thickness of 2 cm to 4 cm and then immersed in 36.5 ° C. water for 15 seconds. The number and size of bubbles generated per unit area are observed through micrographs and snapshots taken after 20 minutes after removing moisture from the surface of the specimen.

Comparing the lubrication degree of the casting sheet prepared in Example 2 and the casting sheet prepared in Comparative Example 1 of the present invention, the lubrication degree of the casting sheet prepared in Comparative Example 1 is 133.0 gf cast in Example 2 The lubrication degree of the sheet is 1089 gf, it can be seen that the lubricity of the casting sheet produced in Example 2 is remarkably excellent.

Comparing the following Example 2 and Example 3 Example 3 is the addition of sodium lauryl ether sulfate in Example 2, the lubricating dispersion effect of the casting sheet prepared in Example 2 and the casting sheet prepared in Example 3 As shown in the graph below obtained in the lubrication test, the graph of Example 2 has a large amplitude and a wide wavelength between curves at the end of the graph, whereas the graph of Example 3 has a small amplitude overall and a narrow and dense curve between curves. . Therefore, it can be seen that the casting sheet of Example 3 to which sodium lauryl ether sulfate was added showed excellent lubricating dispersion effect.

(Graph of Example 2)

(Graph of Example 3)

In addition, when comparing the Comparative Example 1 and Example 2 with the following micrographs and snapshots obtained in the anti-foaming test, it can be seen that the foam of Example 2 is relatively small, which is a siloxane-polyethylene glycol air prepared in Example 1 It can be seen that the coalescing acts to aid in general existing antifoaming agents (eg ANTIFOAM-A).

(Micrograph of Example 2)

(Snapshot of Example 2)

(Micrograph of the comparative example 1)

(Snapshot of Comparative Example 1)

In addition, when comparing the Comparative Example 2 and Example 4 with the following micrographs and snapshots obtained in the anti-foaming test it can be seen that the foam of Example 4 is significantly reduced, which is the siloxane-polyethylene glycol copolymer prepared in Example 1 When used independently, it can be seen that it acts as a vesicle.

(Micrograph of Example 4)

(Snapshot of Example 4)

(Micrograph of the comparative example 2)

(Snapshot of Comparative Example 2)

Claims (8)

Compounds of the general formula (I) as lubricants and defoamers for orthopedic hydrocurable polyurethane prepolymers. R ₁ , R ₂ : alkyl, aryl, aralkyl or unsaturated alkyl, alkoxy R ₃ : alkyl or hydrogen R ₄ : methoxy or R ₅ : Or hydrogen m is an integer 10-200, n is an integer 1-20. The compound of formula (I) according to claim 1, wherein (m is an integer of 10-200, n is an integer of 1-20). Next, a method of preparing general formula (I) by reacting 1 mole of a compound of formula (III) with 1 mole to 2 moles of compound of formula (II). R ₁ , R ₂ : alkyl, aryl, aralkyl or unsaturated alkyl, alkoxy R ₃ : alkyl or hydrogen R ₄ : methoxy or R ₅ : Or hydrogen m is an integer 10-200, n is an integer 1-20. The method of claim 3, Compound of formula (II) having the structure (m is an integer of 10 ~ 200) by reacting a compound of formula (III) (m is an integer of 10 to 200, n is an integer of 1 to 20) A method for producing a compound of formula (I) having a structure. An orthopedic hydraulic polyurethane casting sheet comprising a compound of formula (I) as a lubricant and an antifoaming agent in an orthopedic polyurethane casting sheet. R ₁ , R ₂ : alkyl, aryl, aralkyl or unsaturated alkyl, alkoxy R ₃ : alkyl or hydrogen R ₄ : methoxy or R ₅ : Or hydrogen m is an integer 10-200, n is an integer 1-20. The compound of formula (I) according to claim 5, wherein (m is an integer of 10 to 200, n is an integer of 1 to 20) characterized in that the orthopedic hydrosetting polyurethane casting sheet. The orthopedic polyurethane casting sheet according to claim 5 or 6, wherein sodium alkyl ether sulfate is used in an amount of 2 parts by weight or less based on 100 parts by weight of polyurethane. The orthopedic hydrocurable polyurethane casting sheet according to claim 7, wherein the sodium alkyl ether sulfate is sodium lauryl ether sulfate.